Method of colouring keratin-containing fibres

ABSTRACT

The present invention relates to a method of colouring keratin-containing fibres comprising applying at least one diazonium compound of formula Ia or Ib, wherein R 1  to R 5  are each independently of the others C 1 -C 12 alkyl, C 5 -C 14 aryl, C 5 -C 8 cycloalkyl, C 6 -C 20 aralkyl, C 1 -C 12 alkoxy or C 1 -C 12 alkylthio unsubstituted or substituted by one or more halogen atoms, nitro, cyano or alkoxy groups; or hydrogen, halogen, hydroxy, nitro, COOH, SO 3 H, CN, SCN, C 1 -C 4 alkylsulfonyl, phenylsulfonyl, benzylsulfonyl, di-C 1 -C 4 alkylaminosulfonyl, C 1 -C 4 alkylcarbonylamino, C 1 -C 4 alkoxysulfonyl or dihydroxy-C 1 -C 4 alkylaminosulfonyl and X −  is o − , COO −  or SO 3   − , and at least one coupling component, preferably a a water-soluble to the material to be coloured and causing them to react at a pH in the range of 8 to 12.

The present invention relates to a method of colouring organic material such as keratin, wool, leather, silk, cellulose or polyamides, especially keratin-containing fibres, cotton or nylon, and more especially human hair, using developable dyes and combinations of those developable dyes with other dyes.

Colouring keratin-containing fibres, especially hair, using developable dyes is known. DE-A-30 09 833 describes a method of colouring hair using developable azo dyes wherein a priming cream comprising a diazonium salt and a coupling component is applied at a pH of about 4.5 to the hair and the coupling reaction is then initiated by treatment with an alkaline shampoo. However, because of the considerable change in pH during treatment of the hair, that method is not especially gentle on the skin and scalp.

It has now been found that, when specific azo dyes based on o-diazophenols or o-diazo-naphthols are used in the form of a hair composition, changes in pH during the colouring method can be avoided.

The present invention relates to a method of colouring keratin-containing fibres comprising applying at least one diazonium compound of formula Ia or Ib

wherein R₁ to R₅ are each independently of the others C₁-C₁₂alkyl, C₅-C₁₄aryl, C₅-C₈cyclo-alkyl, C₆-C₂₀aralkyl, C₁-C₁₂alkoxy or C₁-C₁₂alkylthio unsubstituted or substituted by one or more halogen atoms, nitro, cyano or alkoxy groups; or hydrogen, halogen, hydroxy, nitro, COOH, SO₃H, CN, SCN, C₁-C₄alkylsulfonyl, phenylsulfonyl, benzylsulfonyl, di-C₁-C₄alkyl-aminosulfonyl, C₁-C₄alkylcarbonylamino, C₁-C₄alkoxysulfonyl or dihydroxy-C₁-C₄alkylamino-sulfonyl, and X⁻ is O⁻, COO⁻ or SO₃ ⁻, and at least one coupling component, preferably a a water-soluble, in any desired order successively, or simultaneously, to the material to be coloured and causing them to react at a pH in the range of 8 to 12.

When any of the radicals R₁ to R₅ are alkyl, they may be open-chain or branched, unsubstituted or substituted alkyl radicals.

Examples of alkyl groups are methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, neopentyl, n-hexyl, n-octyl, n-decyl, n-dodecyl, trifluoromethyl and chloromethyl.

Suitable, unsubstituted or substituted aryl groups are, for example, phenyl, tolyl, xylyl, mesityl, isityl, naphthyl, anthryl and phenanthryl.

Cycloalkyl is cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl.

Examples of aralkyl groups are benzyl, 1-phenylethyl, 2-phenylethyl, 1,2-diphenylethyl and trityl.

Alkoxy substituents in the compounds of formulae Ia and Ib may have from 1 to 12 carbon atoms, preferably from 1 to 4 carbon atoms. They are, for example, methoxy, ethoxy, propoxy, isopropoxy, n-butoxy, isobutoxy, tert-butoxy, n-pentyloxy or n-hexyloxy. The alkoxy groups may also be substituted, for example by the radicals mentioned as possible substituents for the alkyl groups, especially by hydroxy or by C₁-C₄alkoxy.

Alkylthio substituents also have from 1 to 12 carbon atoms, preferably from 1 to 4 carbon atoms. Examples of alkylthio groups are methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio and tert-butylthio.

Preferred diazonium compounds are compounds of formula Ia or Ib wherein X⁻ is SO₃ ⁻.

Preference is also given to compounds of formula Ia or Ib wherein R₁ to R₅ are each independently of the others hydrogen, halogen, nitro, SO₃H, CN or methyl.

Especially preferred diazonium compounds are the compounds of formulae IIb and IIIb

The diazonium salts of formulae Ia and Ib can be prepared by known methods, for example by diazotisation of the corresponding amines, and some of them are commercially available. They are distinguished by extraordinarily high stability in aqueous solution, that being the case both in the acidic and in the neutral and alkaline ranges.

Suitable coupling components are, for example, the usual coupling components customary in the case of azo dyes and known from the pertinent literature, e.g. those from the benzene series, the naphthalene series, the open-chain active-methylene compounds (such as, for example, acylacetarylamides) and the heterocyclic series.

They are, for example, acylacetarylamides, phenols, naphthols, pyridones, quinolones, pyrazoles, indoles, diphenylamines, anilines, aminopyridines, pyrimidones, naphthylamines, aminothiazoles, thiophenes or hydroxypyridines.

Acetoacetanilides, phenols, anilines, diphenylamines, naphthylamines, indoles, quinolines, pyridones, pyrazoles and aminopyridines are especially suitable.

Such coupling components may carry further substituents, for example amino, alkylamino, dialkylamino, halogen, alkyl, alkoxy, aryl, especially phenyl or naphthyl, or aryloxy, but especially a group imparting water solubility, e.g. hydroxy, carboxy or SO₃H.

The coupling components preferably carry one or two such groups that impart water solubility. Examples of suitable coupling components are as follows:

Those compounds are also known and can be prepared using known methods.

Preferred coupling components are compounds of formula IV, V or VI

Formation of the diazo dye by reaction of the diazonium salt of formula Ia or Ib with the coupling component is carried out in the slightly alkaline range, advantageously in the pH range from 8 to 12, preferably from 9 to 11.

The first stage in the colouring method according to the invention comprises applying either a diazonium compound of formula Ia or Ib or a water-soluble coupling component to the material being coloured. That is accomplished, for example, by immersing the material in an aqueous alkaline solution of the diazonium compound of formula Ia or Ib or of the coupling component.

In the second stage, optionally after rinsing and intermediate drying, the material is treated with the second component, again, for example, by means of immersion in an aqueous alkaline solution of the second component and then rinsing and drying.

It is also possible for the solutions in question to be applied to the material by means of spraying or by similar means, although it must be ensured that there is adequate penetration unless it is desired to colour only the upper layers.

It is also possible to use an aqueous solution comprising a diazonium compound of formula Ia or Ib and the coupling component together. In that case, the pH of the solution should, however, be in the acidic range that is to say at a pH in the range from 1 to 6, preferably from 2 to 4. Only after application of the solution to the fibre material is complete should the pH be increased to a value from 8 to 12, preferably from 9 to 11, in order to bring about the coupling reaction.

The best results in terms of colour intensity and fastness to washing are obtained, however, by means of the embodiment wherein the diazonium salt is applied in the first step, and the coupling component afterwards.

A preferred embodiment is the method according to the invention wherein

-   -   an aqueous solution of diazonium compound of formula(e) (Ia)         or/and (Ib) is applied to the fibre at a pH in the range from 1         to 6, preferably from 2 to 4, or at a pH in the range from 8 to         12, preferably from 9 to 11, and     -   then, usually after 10 minutes to 1 hour,     -   an aqueous solution of a coupling component, preferably one of         formula(e) (IV), (V) or/and (VI), is applied to the fibre at a         pH in the range from 8 to 12, preferably from 9 to 11 and are         caused to react at a pH in the range of 8 to 12, preferably in         the range of 9 to 11.

Another preferred embodiment is the method according to the invention wherein

-   -   an aqueous solution of at least one coupling component,         preferably one of formula(e) (IV), (V) or/and (VI), is applied         to the fibre at a pH in the range from 1 to 6, preferably from 2         to 4, or at a pH in the range from 8 to 12, preferably from 9 to         11, and     -   then, usually after 10 minutes to 1 hour,     -   an aqueous solution of diazonium compound of formula(e) (Ia)         or/and (Ib) is applied to the fibre is applied to the fibre at a         pH in the range from 1 to 6, preferably from 2 to 4, or at a pH         in the range from 8 to 12, preferably from 9 to 11, and     -   caused to react at a pH in the range of 8 to 12, preferably from         9 to 11.

Furthermore preferred is the method according to the invention wherein at least one diazonium compound of formula Ia and/or Ib and at least one coupling component with a pH in the range of 1 to 6, preferably from 2 to 4, are applied to the fibre and are caused to react at a pH in the range of 8 to 12, preferably at a pH in the range of 9 to 11.

The method according to the invention is used especially for colouring hair. The hair may be the hair of wigs or, especially, the living hair of animals and, more especially, humans.

The invention relates also to compositions for carrying out the method according to the invention that comprise

-   (a) at least one diazonium compound of formula Ia or Ib, -   (b) an agent for adjustment of the pH, and -   (c) water.

Preference is given to compositions according to the invention comprising

-   (a) at least one diazonium compound of formula Ia or Ib, -   (b) an agent for adjustment of the pH at a pH in the range from 1 to     6, preferably from 2 to 4, or at a pH in the range from 8 to 12,     preferably from 9 to 11, and -   (c) water.

The present invention relates also to compositions comprising

-   (a) at least one diazonium compound of formula Ia or Ib, -   (b) at least one coupling component and, especially, -   (c) an agent for adjustment of the pH, and -   (d) water.

Preference is given to compositions according to the invention that comprise

-   (a) at least one diazonium compound of formula Ia or Ib, and -   (b) at least one coupling component, and that have a pH at a pH in     the range from 1 to 6, preferably from 2 to 4.

Special preference is given to compositions comprising as coupling component at least one compound of formula(e) (IV), (V) or/and (VI).

Special preference is also given to compositions comprising as diazonium compound at least one compound of formula(e) (IIb) or/and (IIIb)

Very special preference is given to compositions comprising, as coupling component, at least one compound of formula(e) (IV), (V) or/and (VI) and, as diazonium compound, at least one compound of formula(e) (IIb) or/and (IIIb).

Special preference is given to compositions for colouring hair. Further additives that are suitable for such compositions include additives that are customary in hair-colouring, for example further dyes, surfactants, solvents, perfumes, polymeric adjuvants, thickeners and light stabilisers.

In a further preferred embodiment of the method according to the invention, a composition according to the invention is applied to the material to be coloured and is then caused to react at a pH in the range from 8 to 12.

The multiplicity of shades of the dye, which results by the method according to the present invention, can be increased by combination with other dyes.

The present invention relates also to methods of the colouration of hair with combination of diazonium compound of formula Ia or Ib and a coupler compounds and/or at least one further dye.

Further dyes are for example direct dyes, oxidation dyes; dye precursor combinations of a coupler compound and a diazotized compound, or a capped diazotized compound; and/or cationic reactive dyes.

Direct dyes are natural or synthetic; they are uncharged, cationic or anionic, such as acid dyes.

Oxidation dye denotes also for oxidation dye precursors, which are from the group of the developer and coupler compounds. Wherein the coupler compounds denotes also to the addition salts thereof with an acid.

In the context of the invention the single classes of dyes comprise the dyes defined in the Color Index of the Society of Textile Chemist and Colorist.

In the context of the present invention compositions, formulation, methods and methods comprise at least a single dye of formula Ia or Ib and at least a single coupler compound.

Preferred direct dyes for the combination with the method according to the present invention are described.

Directs dyes are for example described in “Dermatology”, edited by Ch. Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7, Ch. Zviak, The Science of Hair Care, chapter 7, pages 248-250, and

in “Europäisches Inventar der Kosmetikrohstoffe”, 1996, published by The European Commission, obtainable in diskette form from the Bundesverband der deutschen Industrie-und Handelsunternehmen für Arzneimittel, Reformwaren und Körperpflegemittel e.V., Mannheim.

More preferred direct dyes, especially for semi permanent dyeing, are:

2-Amino-3-nitrophenol, 2-Amino-4-hydroxyethylamino-anisole sulfate, 2-Amino-6-chloro-4-nitrophenol, 2-Chloro-5-nitro-N-hydroxyethylene-p-phenylendiamine, 2-Hydroxyethyl-picramic acid, 2,6-Diamino-3-((pyridine-3yl)-azo)pyridine, 2-Nitro-5-glyceryl-methylaniline, 3-Methylamino-4-nitro-phenoxyethanol, 4-Amino-2-nitrodiphenyleneamine-2′-carboxilic acid, 6-Nitro-1,2,3,4,-tetrahydroquinoxaline, 4-N-Ethyl-1,4-bis(2′-hydroxyethylamino-2-nitrobenzene hydrochloride, 1-Methyl-3-nitro-4-(2′-hydroxyethyl)-aminobenzene, 3-Nitro-p-hydroxyethyl-aminophenol, 4-Amino-3-nitrophenol, 4-Hydroxypropylamine-3-nitrophenol, Hydroxyanthryl-aminopropylmethyl morphlino methosulfat, 4-Nitrophenyl-aminoethylurea, 6-Nitro-p-toluidine, Acid Blue 62, Acid Blue 9, Acid Red 35, Acid Red 87 (Eosin), Acid Violet 43, Acid Yellow 1, Basic Blue 3, Basic Blue 6, Basic Blue 7, Basic Blue 9, Basic Blue 12, Basic Blue 26, Basic Blue 99, Basic Brown 16, Basic Brown 17, Basic Red 2, Basic Red 22, Basic Red 76, Basic Violet 14, Basic Yellow 57, Basic Yellow 9, Disperse Blue 3, Disperse Orange 3, Disperse Red 17, Disperse Violet 1, Disperse Violet 4, Disperse Black 9, Fast Green FCF, HC Blue 2, HC Blue 7, HC Blue 8, HC Blue 12, HC Orange 1, HC Orange 2, HC Red 1, HC Red 10-11, HC Red 13, HC Red 16, HC Red 3, HC Red BN, HC Red 7, HC Violet 1, HC Violet 2, HC Yellow 2, HC Yellow 5, HC Yellow 5, HC Yellow 6, HC Yellow 7, HC Yellow 9, HC Yellow 12, HC Red 8, Hydroxyethyl-2-nitro-p-toluidine, N,N-Bis-(2-Hydroxyethyl)-2-nitro-p-phenylendiamine, HC Violet BS, Picramic Acid, Solvent Green 7.

Also, more preferred for combinations with the method according to the present invention are cationic azo dyes, for example according to GB-A-2 319 776 as well as the oxazine dyes described in DE-A-299 12 327 and mixtures thereof with the other direct dyes mentioned therein.

Furthermore preferred for combinations with the method according to the present invention are direct dyes, which are suitable as single dye or in combination with other direct dyes or oxidative dyes and oxidization agents, especially for semi permanent dyeing and permanent dyeing, are:

Disperse Violet 4, Picramic acid, N,N′-Bis-(2-Hydroxyethyl)-2-nitro-p-phenylendiamine, HC Yellow No. 5, HC Blue No. 2, HC Yellow No. 2,2-Chloro-5-nitro-N-hydroxyethyl-p-phenylendiamine, HC Red No. 3,4-Amino-3-nitrophenol, Basic Blue 99,2-Hydroxyethyl Picramic acid, HC Yellow No. 6, Hydroxyethyl-2-nitro-p-toluidine, 2-Amino-6-chloro-4-nitrophenol, 4-Hydroxypropylamino-3-nitrophenol, Basic Red 2, HC Red No. 16 and HC Blue No. 16.

Further preferred cationic dyes for the combination with the method according to the present invention are described.

Preferred cationic dyes are described

-   -   in WO 95/01772, especially on page 2, line 7 to page 4, line 1,         and especially on page 4, line 35 to page 8, line 21 and on         pages 11 to 27, or     -   in WO 01/66646, especially on page 1, line 18 to page 3, line         16, and preferred from page 16, line 20 to page 22, and cationic         dyes as described on pages 10 to 17, or     -   in EP 970 685, especially on page 2, line 44 to page 9, line 56         and preferably on page 9, line 58 to page 48, line 12, or     -   direct dyes are described in DE-A-19 713 698, especially page 2,         line 61 to page 3, line 43, or     -   direct dyes and oxidizing agent are described in WO 97/20545,         especially on page 1, lines 4 to 10, in particular on page 3,         lines 24 to 32, and on pagel 1, line 6 to page 13, line 19,         especially with direct dyes are described on page 5, line 28 to         page 8, line 20, or     -   cationic dyes and anionic UV-absorbers are described in EP 1 166         752, especially on page 3, line 20 to page 4, line 21, in         particular with UV absorber on page 4, lines 26 to 3, and         especially on page7, line 47 to page 9, line 56.

Most preferred for the combination with the method according to the present invention are are cationic dyes such as Basic Yellow 87, Basic Orange 31 or Basic Red 51, or cationic dyes as described in WO 01/66646, especially cationic dye of example 4, or cationic dyes as described in WO 02/31056, especially cationic dye of example 6, compound of formula 106.

Further preferred for combination with the method according to the invention are cationic nitroaniline and anthraquinone dyes, for example those described in the following patent specifications: U.S. Pat. No. 5,298,029, especially in column 2, line 33 to column 5, line 38; U.S. Pat. No. 5,360,930, especially in column 2, line 38 to column 5, line 49; U.S. Pat. No. 5,169,403, especially in column 2, line 30 to column 5, line 38; U.S. Pat. No. 5,256,823, especially in column 4, line 23 to column 5, line 15; U.S. Pat. No. 5,135,543, especially in column 4, line 24 to column 5, line 16; EP-A-818 193, especially on page 2, line 40 to page 3, line 26; U.S. Pat. No. 5,486,629, especially in column 2, line 34 to column 5, line 29; and EP-A-758 547, especially on page 7, line 48 to page 8, line 19.

Further preferred for combination with the method according to the invention are mixtures of cationic dyes with other dyes:

-   -   mixtures of at least two cationic dyes as described in WO         95/01772, especially on page 8, line 34 to page 10, line 22 with         the given preferences, or     -   combinations of Pyrazolo-[1,5-a]-pyrimidines with at least one         cationic dye as described in EP 998,908, especially on page 2,         line 34 to line 42, with preferred Pyrazolo-[1,5-a]-pyrimidines         as described in EP 998,908, especially on page 2, line 48 to         page 4, line 3, and with preferred cationic direct dyes as         described in EP 998,908, especially on page 4, line 22 to page         47, line 24, or     -   combinations of cationic dyes as described in FR-2788432,         especially on page 53, line 1 to page 63, line 23, especially a         combination of cationic dyes with Arianors in FR-2788432,         especially on pages 51 to 52, or especially a combination with         at least one Basic Brown 17, Basic brown 16, Basic Red 76 and         Basic Red 118, and/or at least one Basic Yellow 57, and/or at         least one Basic Blue 99, or     -   combinations of direct dyes and/or an oxidation dye and         oxidizing agents in the form of permanent-wave fixing solution,         especially with direct dyes as described in DE-A-19 713 698,         especially page 4, line 65 to page 35, line 59, or     -   combinations of cationic dyes and an oxidation dye of the         developer compound type and oxidizing agents as described in EP         850 638, especially on page 2, line 27 to page 7, line 46 and         preferred on page 7, line 20 to page 9, line 26, or     -   combinations of an extemporaneous mixture of a composition (A)         containing one or more oxidation dye precursors and optionally         one or more couplers, and of a composition (B), in powder form,         containing one or more direct dye, preferably cationic,         optionally dispersed in an organic pulverulent excipient and/or         a mineral pulverulent excipient, and a composition (C)         containing one or more oxidizing agent as described in U.S. Pat.         No. 6,190,421, especially in column 2, lines 2 to 1, and         preferably with oxidation dye precursors as described in column         2, line 35 to column 5, line 13, and preferably with direct dyes         as described in column 5, line 30 to column 7, line 14, or     -   a ready-to-use composition comprising, at least one oxidation         base, at least one cationic direct dye and at least one enzyme         of 2-electron oxidoreductase type in the presence of at least         one donor for the said enzyme as described in U.S. Pat. No.         6,228,129, especially in column 26, line 26 to column 27, line 9         with cationic direct dyes as described in column 8, line 17 to         column 13, line 65, especially those as described in column 20,         line 11 to line 19, in column 23, line 61 to column 24, line 25,         or     -   compositions of at least one direct cationic dye and at least         one nitrated benzene dye as described in WO 99/20235 on page 2,         line 1 to page 7, line 9, and on page 39, line 1 to page 40b         line 11, with cationic direct dyes as described on page 8, line         12 to page 25 line 6, and nitro benzene direct dyes as described         on page 26, line 7 to page 30, line 15, or     -   compositions of at least one direct cationic dye and at least         one autooxidisable oxidation dye, especially benzene, indol and         indoline derivatives as described in WO 99/20234, with in         preferred direct dyes as given on page 2, line 17 to page 26,         line 4, and autooxidisable oxidation dye as described especially         on page 26, line 10 to page 28, line 15, or     -   oxidation dyeing compositions of at least one direct dye and at         least one meta-Aminophenol derivative and at least one developer         compound and an oxidizing agent as described in EP 850 636,         especially on page 5, line 41 to page 7, line 52, and preferably         on page 19, line 50 to page 22, line 12, with preferred direct         dye as described on page 18, lines 1 and 2 in connection with         page 7, line 53 to page 17, line 55, and with preferred         meta-Aminophenol derivatives as described on page 7, line 47 to         line 52, and with preferred developer compounds as described on         page 6, line 10 to page 7, line 46, or     -   oxidation dyeing compositions of at least one direct dye and at         least one developer compound selected from the group of         para-Phenylenediamine derivatives and Bis-Phenylalkylenediamine         and, and at least one coupler compound selected from the group         of meta-Diphenols and an oxidizing agent, as described in         EP-A-850 637, especially on page 6, line 50 to page 8, line 44,     -   oxidation dyeing compositions with cationic couplers, as         described in WO 99/48856, especially on page 9, line 16 to page         13, line 8, and page 11, line 20 to page 12, line 13, or     -   cationic dye and e.g. a pyrazolo-(1,5-a)-pyrimidine derivatives,         as described in EP 998 908, especially on page 2, line 34 to         page 4, line 23, or     -   arianoren and/or oxidative dyes, as described in FR-2 788 432,         especially on page 2, line 16 to page 3, line 16, and page 5,         line 19 to page 14, line 8, and combinations with cationic dyes         as described on page 14, line 23 and following, or     -   oxidative dye precursors (unsaturated aldehyde and coupler         compounds), as described in German Patent Application 197 172         24, especially unsaturated aldehydes as described on page 2,         line 50 to line 66 and page 3 line 8 to line 12 are used as         developer compounds, and primary and secondary amino group         compounds, nitrogen-containing heterocyclic compounds, amino         acids, oligopeptids, aromatic hydroxy compounds, CH-active         compounds as described on page 3, line 42 to page 5 line 25 are         used as coupler compounds.

Also cationic azo dyes, e.g. according to GB-A-2 319 776, as well as the oxazine dyes described in DE-A-29 912 327 and mixtures thereof with the other direct dyes mentioned therein, can likewise readily be combined.

More preferred are cationic dyes such as Basic Yellow 87, Basic Orange 31 or Basic Red 51, or as described in WO 01/66646, especially cationic dye of example 4, or as described in WO 02/31056, especially cationic dye of example 6, compound of formula 106.

Especially preferred direct dye mixtures comprising a dye of formula (1) of WO 01/66646, especially a direct dye of example 4, and/or or a dye of formula (2) of WO 02/31056, especially a direct dye of example 6, and/or Basic Yellow 87, and/or Basic Red 51, and/or Basic Orange 31.

No particular limitation is imposed on the acid dye used in the present invention so far as it is a water-soluble acid dye.

For the purpose of further modification of color shades, the method of colouring according to the invention comprise customary acid dyes, for example from the group of the compounds known by the international names (Color index), or trade names.

Preferred acid dyes are described in U.S. Pat. No. 6,248,314, they include Red Color No.120, Yellow Color No. 4, Yellow Color No. 5, Red Color No. 201, Red Color No. 227, Orange Color No. 205, Brown Color No. 201, Red Color No. 502, Red Color No. 503, Red Color No. 504, Red Color No. 506, Orange Color No. 402, Yellow Color No. 402, Yellow Color No. 406, Yellow Color No. 407, Red Color No. 213, Red Color No. 214, Red Color No. 3, Red Color No. 104, Red Color No. 105(1), Red Color No. 106, Green Color No. 2, Green Color No. 3, Orange Color No. 207, Yellow Color No. 202(1), Yellow Color No. 202(2), Blue Color No. 202, Blue Color No. 203, Blue Color No. 205, Blue Color No. 2, Yellow Color No. 203, Blue Color No. 201, Green Color No. 201, Blue Color NO. 1, Red Color No. 230(1), Red Color No. 231, Red Color No. 232, Green Color No. 204, Green Color No. 205, Red Color No. 401, Yellow Color No. 403(1), Green Color No. 401, Green Color No. 402, Black Color No. 401 and Purple Color No. 401, especially Black Color No. 401, Purple Color 401, Orange Color No. 205.

These acid dyes may be used either single or in any combination thereof.

Preferably they are incorporated in a proportion of 0.001-5% by weight (hereinafter indicated merely by “%”), particularly 0.005-4%, more particularly 0.2-3% based on the total weight of the composition, from the viewpoint of practical use in that a sufficient hair-dyeing effect is achieved, and the hand skin is scarcely smeared.

Further preferred for combination with the method according to the invention are uncharged dyes, for example from the group of the nitroanilines, nitrophenylenediamines, nitroaminophenols, anthraquinones, indophenols, phenazines, phenothiazines, bispyrazolons or bispyrazol aza derivatives or methines.

In addition, preferred for combination with the method according to the invention are oxidation dyes.

Preferred oxidation dyes are described for example in

-   -   German Patent Application 19 94 450, especially on page 6, line         6 to line 64, or     -   German Patent Application 19 959 479, especially in column 2,         line 6 to column 3, line 11, or     -   in the series “Dermatology”, edited by Ch. Culnan, H. Maibach,         Verlag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7, Ch.         Zviak, The Science of Hair Care, chapter 8, on pages 264-267         (oxidation dyes), or     -   in German Patent Application 19 717 224; unsaturated aldehydes         as described on page 2, line 50 to line 66 and on page 3 line 8         to line 12 are used as developer compounds, and primary and         secondary amino group compounds, nitrogen-containing         heterocyclic compounds, amino acids, oligopeptids, aromatic         hydroxy compounds, CH-active compounds as described on page 3,         line 42 to page 5 line 8 are used as coupler compounds.

Preferred oxidation dye precursors of the developer type are for example primary aromatic amines, which are substituted in the para- or ortho-position with a substituted or unsubstituted hydroxy- or amino residue, or diaminopyridine derivatives, heterocyclic hydrazones, 4-aminopyrazol derivatives, 2,4,5,6-tetraaminopyrimidin derivatives, or unsaturated aldehydes as described in German Patent Application 19 717 224, especially on page 2, line 50 to line 66 and on page 3 line 8 to line 12, or cationic developer compounds as described in WO 00/43367, especially on page, 2 line 27 to page 8, line 24, in particular on page 9, line 22 to page 11, line 6.

Also very suitable for combination with the method according to the invention are developer dyes in their physiological compatible acid addition salt form, such as hydrochloride or sulfate. Developer dyes which have aromatic OH substituents are also suitable in their salt form with base, such as alkalimetalphenolates.

Preferred developer compounds are:

1,4-diamino-benzene (p-phenylendiamine), 1,4-diamino-2-methyl-benzene (p-toluylendiamine), 1,4-diamino-2,6-dimethyl-benzene, 1,4-diamino-2,5-dimethyl-benzene, 1,4-diamino-2,3-dimethyl-benzene, 2-chloro-1,4-diaminobenzene, 4-phenylamino-aniline, 4-di-methylamino-aniline, 4-diethylamino-aniline, hydroxyethyl-p-phenylendiamine, 1-(2′-hydroxy-ethyl)-2,5-diaminobenzene, N,N-bis-(2-hydroxyethyl)-p-phenylendiamine, 4-[(2-methoxyethyl)amino]-aniline, 4-[(3-hydroxypropyl)amino]-aniline, hydroxypropyl-bis-(N-hydroxyethyl-p-phenylenediamine) hydrochloride, 1,4-diamino-2-(2-hydroxyethyl)-benzene, 1,4-diamino-2-(1-methylethyl)-benzene, 2-(2,5-diaminophenoxy)-ethanol, 1,3-bis[(4-aminophenyl)(2-hydroxyethyl)amino]-2-propanol, bis-(2-hydroxy-5-aminophenyl)-methane, 1,4-bis-(4-aminophenyl)-diazacycloheptane, 1,8-bis(2,5-diaminophenoxy)-3,6-dioxaoctan, 1,10-bis-(2,5-diaminophenyl)-1,4,7,10-tetraoxadecane, hydroxyethyl-3,4-methylenedioxyaniline, p-aminophenol, o-aminophenol, m-aminophenol, 2-amino-6-methyl-phenol, 4-methylaminophenol sulfate, 4-amino-m-cresol, 6-amino-m-cresol, 6-amino-m-cresol, 2-amino-4-hydroxyethylaminoanisole, 2-amino-5-methyl-phenol, 4-amino-3-methylphenol, 4-methylamino-phenol, 2-aminomethyl-4-aminophenol, 4-amino-2-[(2-hydroxyethyl)-amino]methyl-phenol, 4-amino-2-(2-hydroxyethoxy)-phenol, 4-amino-2-(methoxymethyl)-phenol, 4-amino-2-(2-hydroxyethyl)-phenol, 2-hydroxymethylamino-4-aminophenol, bis-(4-aminophenyl)amine, 4-amino-3-fluorphenol, 2-hydroxymethyl-4-aminophenol, 4-amino-2-(diethylamino)-methyl)-phenol, 5-amino-salicylsäure, 2,5-diamino-pyridine, 2-amino-3-hydroxy-pyridine, 2,6-dimethoxy-3,5-diamino-pyridine, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine, 2,4-dihydroxy-5,6-diaminopyrimidine, 2-dimethylamino-4,5,6-triaminopyrimidine, 2,5,6-triamino-4-(1H)-pyrimidone, further 4,5-diaminopyrazol derivatives as described in EP 0 740 741 or WO 94/08970, especially 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazol, 4,5-diamino-1-(1-methylethyl)-1H-pyrazol, 4,5-diamino-1-[(4-methylphenyl)methyl]-1H-pyrazol, 1-[(4-chlorophenyl)methyl]-4,5-diamino-1H-pyrazol, 4,5-diamino-1-methyl-1H-pyrazol.

More preferred developer dyes are p-phenylendiamine, p-toluylendiamine, p-aminophenol, m-aminophenol, o-aminophenol, N,N-bis-(2-hydroxyethyl)-p-phenylendiamine sulfate, 2-amino-4-hydroxyethylaminoanisole sulfate, hydroxyethyl-3,4-methylenedioxyaniline, 1-(2′-hydroxyethyl)-2,5-diaminobenzene, 2,6-dimethoxy-3,5-diamino-pyridine, hydroxypropyl-bis-(N-hydroxyethyl-p-phenylenediamine) hydrochloride, hydroxyethyl-p-phenylendiamine sulfate, 4-amino-3-methylphenol, 4-methylaminophenol sulfate, 2-aminomethyl-4-aminophenol, 4,5-diamino-1-(2-hydroxyethyl)-1H-pyrazol, 4-amino-m-cresol, 6-amino-m-cresol, 5-amino-6-chloro-cresol, 2,4,5,6-tetraaminopyrimidine, 2-hydroxy-4,5,6-triaminopyrimidine, 4-hydroxy-2,5,6-triaminopyrimidine sulfate.

Preferred oxidation dye precursors of the coupler type are for example m-phenylendiamine derivatives, naphthole, resorcine and resorcine derivatives, pyrazolone and m-aminophenol derivatives.

Especially preferred coupler compounds are N-(3-dimethylamino-phenyl)-urea, 4-amino-2-hydroxytoluene, 2-methyl-5-hydroxyethylaminophenol, 2,4-diaminophenoxyethanol, 2-amino-4-[(2-hydroxyethyl)amino]-anisole, p-aminophenol, m-aminophenol and its derivatives, especially 5-amino-2-methylphenol, 5-(3-hydroxypropylamino)-2-methylphenol, 3-amino-2-chloro-6-methylphenol, 2-hydroxy-4-aminophenoxyethanol, 2,6-dimethyl-3-aminophenol, 3-trifluoroacetylamino-2-chloro-6-methylphenol, 5-amino-4-chloro-2-methylphenol, 5-amino-4-methoxy-2-methylphenol, 5-(2′-hydroxyethyl)-amino-2-methylphenol, 3-(diethylamino)-phenol, N-cyclopentyl-3-aminophenol, 1,3-dihydroxy-5-(methylamino)-benzene, 3-(ethyl-amino)-4-methylphenol and 2,4-dichloro-3-aminophenol,

-   -   o-aminophenol and its derivatives, such as         5-methyl-2-(1-methylamino)-phenol, 3-di-methylamino-phenol,         3-diethylamino-phenol, 5-amino-2-methyl-phenol,         5-amino-4-fluor-2-methyl-phenol,         5-amino-4-methoxy-2-methyl-phenol,         5-amino-4-ethoxy-2-methyl-phenol, 3-amino-2,4-dichlor-phenol,         5-amino-2,4-dichlor-phenol, 3-amino-2-methyl-phenol,         3-amino-2-chlor-6-methyl-phenol, 3-amino-phenol,         2-[(3-hydroxy-phenyl)amino]-acetamide,         5-[(2-hydroxyethyl)amino]-2-methyl-phenol,         3-[(2-hydroxy-ethyl)amino]-phenol,         3-[(2-methoxyethyl)amino]-phenol, 5-amino-2-ethyl-phenol,         2-(4-amino-2-hydroxyphenoxy)-ethanol,         5-[(3-hydroxypropyl)amino]-2-methyl-phenol,         3-[(2,3-dihydroxypropyl)amino]-2-methyl-phenol,         3-[(2-hydroxyethyl)amino]-2-methyl-phenol,     -   m-diaminobenzene and its derivatives such as         2,4-diaminophenoxyethanol, 1,3-bis-(2,4-diaminophenoxy)-propane,         1-methoxy-2-amino-4-(2′-hydroxyethylamino)-benzene,         1,3-bis-(2,4-diaminophenyl)-propane,         3-[(2-aminoethyl)amino]-aniline,         1,3-di(2,4-diaminophenoxy)-propane,         1,3-diamino-2,4-dimethoxy-benzene,         2,6-bis(2-hydroxyethyl)amino-toluene,         di(2,4-diaminophenoxy)-methane,         3-[di(2-hydroxyethyl)amino]-aniline,         2,6-bis-(2-hydroxyethylamino)-1-methylbenzene and         1-amino-3-bis-(2′-hydroxyethyl)-aminobenzene,     -   o-diaminobenzene and its derivatives such as 3,4-diaminobenzoic         acid and 2,3-diamino-1-methylbenzene,         2,4-diamino-1-fluor-5-methyl-benzene,         2,4-diamino-1-methoxy-5-methyl-benzene,         1-(2-aminoethoxy)-2,4-diaminobenzene,         2-amino-1-(2-hydroxyethoxy)-4-methylamino-benzene,         2,4-diaminophenoxy-acetic acid,         2,4-di-amino-1-ethoxy-5-methyl-benzene,         3-[(2-hydroxyethyl)amino]-aniline, 3,4-diamino-benzoic acid,         3,4-dihydro-6-hydroxy-1,4(2H)-benzoxazine,         6-amino-3,4-dihydro-1,4(2H)-benzoxazine,         2,4-diamino-1,5-di(2-hydroxyethoxy)-benzene,         2,4-diamino-1-(2-hydroxyethoxy)-5-methyl-benzene,         4-amino-2-di[(2-hydroxyethyl)amino]-1-ethoxy-benzene         2,4-di[(2-hydroxyethyl)amino]-1,5-dimethoxy-benzene,         3,4-dihydro-6-hydroxy-1,4(2H)-benzoxazine,         6-amino-3,4-dihydro-1,4(2H)-benzoxazine,     -   di- or trihydroxybenzene derivatives such as resorcine,         resorcinmonomethylether, 2-methylresorcine, 5-methylresorcine,         2,5-dimethylresorcine, 1-chloro-2,4-dihydroxy-benzene,         2-chlororesorcine, 4-chlororesorcine,         2,6-dihydroxyethylaminotoluene,         1,2-dichlor-3,5-dihydroxy-4-methyl-benzene,         1,5-dichlor-2,4-dihydroxy-benzene,         1,3-di-hydroxy-2-methyl-benzene, pyrogallol and         1,2,4-trihydroxybenzene,     -   pyridine derivatives such as 2,6-diamino-pyridine,         2,6-dihydroxypyridine, 2-amino-3-hydroxypyridine,         2-amino-5-chloro-3-hydroxypyridine,         5-amino-4-chloro-2-methyl-phenol, 3-diamino-6-methoxy-pyridine,         3-amino-2-methylamino-6-methoxypyridine,         2,6-dihydroxy-3,4-dimethylpyridine,         2,6-dihydroxy-4-methylpyridine, 2,6-diamino-pyridine,         2,3-diamino-6-methoxypyridine,         2,6-diamino-3,5-dimethoxy-pyridine, and         3,5-diamino-2,6-dimethoxypyridine,     -   naphthaline derivatives such as 1-naphthol, 2-methyl-1-naphthol,         2-hydroxymethyl-1-naphthol, 2-hydroxyethyl-1-naphthol,         1,5-dihydroxynaphthaline, 1,6-dihydroxy-naphthaline,         1,7-dihydroxynaphthaline, 1,8-dihydroxynaphthaline,         2,7-dihydroxy-naphthaline and 2,3-dihydroxynaphthaline,         2-methyl-1-naphthol-acetat,     -   morpholine derivatives such as 6-hydroxybenzomorpholine and         6-aminobenzo-morpholine,     -   chinoxaline derivatives such as         6-methyl-1,2,3,4-tetrahydrochinoxaline,     -   pyrazol derivatives such as -phenyl-3-methylpyrazol-5-one,         3-methyl-1-phenyl-5-pyrazolone,     -   indol derivatives such as 4-hydroxyindol, 5-hydroxy-indol,         6-hydroxyindol and 7-hydroxyindol, 2,3-indolindione,         5,6-dihydroxy-indol, 5,6-dihydroxy-indoline,     -   methylendioxybenzene derivates such as         1-hydroxy-3,4-methylendioxybenzene,         1-amino-3,4-methylendioxybenzene and         1-(2′-hydroxyethyl)-amino-3,4-methylen-dioxybenzene,         3,4-methylendioxy-phenol, 3,4-methylendioxy-aniline,         5-[(2-hydroxyethyl)amino]-1,3-benzodioxol,         6-brom-1-hydroxy-3,4-methylendioxy-benzene, or     -   cationic coupler compounds as described in FR 2 794 644,         especially on page 11, line 20 to page 15, line 34, and on page         17, lines 4 to 12, page 178, line 33 to page 18, line 24.

More especially preferred coupler compounds are toluene-2,5-diamine sulfate, 1-naphthol, 1,5-, 2,7- and 1,7-dihydroxynaphthaline, 3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, resorcinol, 4-chlororesorcine, 2-chloro-6-methyl-3-aminophenol, 2,6-di-hydroxyethylaminotoluene, 2-methyl-5-dihydroxyethylaminophenol, 2,4-diaminophenoxy-ethylol hydrochloride, 2-methylresorcine, 5-methylresorcine, 2,5-dimethylresorcine, 3,4-methylenedioxyphenol, 2-amino-4-hydroxyethylaminoanisole sulfate, 2,6-di-(beta -hydroxy-ethylamino)-toluene, 4-amino-2-hydroxytoluene, 6-hydroxyindol, 2-amino-3hydroxypyridine, 2,6-dimethoxy-3,5-pyridinediamine hydrochloride and 2,6-dihydroxy-3,4-dimethylpyridine.

Most preferred coupler compounds are 2-chloro-6-methyl-3-aminophenol, 5-amino-2-methylphenol, 2-amino-3-hydroxypyridine, 2,6-di-(beta -hydroxyethylamino)-toluol, 2-methylresorcine and 1-naphthol.

The developer/-coupler combination 2,4,5,6-Tetraaminopyrimidine and 2-Methylresorcine are preferred for assessing of red shades, or

-   p-Toluenediamine and 4-Amino-2-hydroxytoluene are preferred for     assessing of blue-violet shades, or -   p-Toluenediamine and 2-Amino-4-hydroxyethylaminoanisole are     preferred for assessing of blue shades, or -   p-Toluenediamine and 2,4-Diamino-phenoxyethynol are preferred for     assessing of blue shades, or -   3-Methyl-4-aminophenol and 4-Amino-2-hydroxytlouene are preferred     for assessing of orange shades, or -   p-Toluenediamine and resorcine are preferred for assessing of     brown-green shades, or -   p-Toluenediamine and 1-Naphthol are preferred for assessing of     blue-violet shades, or -   p-Toluenediamine and 2-methylresorcine are preferred for assessing     of brown-gold shades.

Further, the colouring method according to the present invention may also contain autooxidizable compounds, such as, for example benzene, indol, or indoline, especially 5,6-dihydroxyindol or 5,6-dihydroxyindoline derivatives as described in WO 99/20234, especially on page 26, line 10 to page 28, line 15, or in WO 00/28957 on page 2, third paragraph.

Preferred autooxidizable benzene derivatives are:

1,2,4-trihydroxybenzene, 1-methyl-2,4,5-trihydroxybenzene, 2,4-diamnio-6-methylphenol, 2-amino-4-methylaminophenol, 2,5-diamino-4-methyl-phenol, 2,6-diamino-4-diethylamino-phenol, 2,6-diamino-1,4-dihydroxybenzen, and the salts of these compounds, which are accessible with acid.

Preferred autooxidizable indol derivatives are:

5,6-dihydroxyindol, 2-methyl-5,6-dihydroxyindol, 3-methyl-5,6-dihydroxyindole, 1-methyl-5,6-dihydroxyindol, 2,3-dimethyl-5,6-dihydroxyindol, 5-methoxy-6-dihydroxyindol, 5-acetoxy-6-hydroixyindol, 5,6-diacetoxyindol, acid of 5,6-dihydroxyindol-2-carbonacid, and the salts of these compounds, which are accessible with acid.

Preferred autooxidizable indoline derivatives are:

5,6-dihydroxyindoline, 1-methyl-5,6-dihydroxyindoline, 1-ethyl-5,6-dihydroxyindoline, and the salts of these compounds, which are accessible with acid.

The colouring method according to the present invention also concerns the joint use of at least two different developers and at least one coupler compound, or combinations of at least two different couplers and at least one developer compound. Such combinations are for example described in German Patent Application 197 172 24, especially on page 3, line 31 to page 5, line 8.

In addition, the colouring method according to the present invention may also encompass combinations with naturally occurring dyes, such as, for example, henna red, henna neutral, henna black, camomile blossom, sandalwood, black tea, Rhamnus frangula bark, sage, campeche wood, madder root, catechu, sedre and alkanet root. Such colouring methods are described, for example, in EP-A-404 868, especially on page 3, line 55 to page 4, line 9.

Further, the dyes, dye precursors according to the colouring method of the present invention can be applied as formulation.

The present invention also concerns also compositions, especially formulations, which are used for the colouration of keratin fibres, especially human hair.

The formulations are applicable on human-hair in different technical forms. The specific technical form may be chosen in view of the envisaged application and/or dye or dye composition. Technical forms of formulation are for example a solution, especially a thickened watery or watery alcoholic solution, a cream, shampoo, powder, foam, a gel, or an emulsion.

Preferred forms of formulations are ready to use compositions or a multi-compartment dyeing device or ‘kit’ or any of the multi-compartment packaging systems with compartments as described for example as described in U.S. Pat. No. 6,190,421, column 2, lines 16 to 31. The dingele compartments may have different technical forms, for example a solution, especially a thickened watery or watery alcoholic solution, a cream, shampoo, powder, foam, a gel, or an emulsion.

It is of advantage to prepare compositions of dyes, which are not stable to reduction, with oxidizing agent free compositions just before the dyeing method.

In a further preferred embodiment of the present invention single dyes and/or adjuvants, or compositions of dyes and/or adjuvants are formulated in powder form.

The colouring compositions for carrying out the method according to the invention may furthermore comprise any active ingredient, additive or adjuvant known for such preparations.

Adjuvants that are suitable for such formulations are in general customary in the field hair-colouring, such as for example surfactants or tensides, solvents, bases, acids, perfumes, polymeric adjuvant, thickeners and light stabilisers.

Preferred combinations of the colouring compositions for carrying out the method according to the invention with adjuvant used in the colouring of hair, are

-   -   combination of direct dyes with oxidizing agents to achieve         lightened colouration; wherein oxidizing agents especially         described in WO 97/20545, especially page 9, lines 5 to 9,     -   combination of direct dyes and/or an oxidation dye and oxidizing         agents in the form of permanent-wave fixing solution, especially         oxidizing agents as described in DE-A-19 713 698, especially         page 4, lines 52 to 55, or EP-A-1 062 940, especially page 6,         lines 41 to 47, (and in the equivalent WO 99/40895),     -   oxidation dyes in the presence of oxidoreductase enzyme, as         described in WO 99/17730, especially page 4, line 11 to page 13,         line 28, and WO 99/36034, especially pages 3 to 15,     -   combination of cationic dyes with polyols or polyethers; polyols         or polyethers as described in EP-A-962 219, especially page 27,         lines 14 to 38,     -   thickening polymers, as described in EP-A-970 684, especially         page 48, line 16 to page 51, line 4,     -   sugar-containing polymers, as described in EP-A-970 687,         especially page 28, line 17 to page 29, line 23,     -   quaternary ammonium salts, as described in WO 00/10517,         especially page 44, line 16 to page 46, line 23,     -   anionic surfactants, as described in WO 00/10518, especially         page 45, line 11 to page 48, line 3,     -   non-ionic surfactants, as described in WO 00/10519, especially         page 45, line 11 to page 50, line 12, or     -   silicones, as described in WO 00/12057, especially page 45, line         9 to page 55, line 2.     -   oxidative agent or laser and direct dyes, as described in EP-920         856, especially on page 2, line 31 to page 53 line 36, and on         page 49, line 38 to page 50, line 41, with direct dyes as         described on page 3, line 54 to page 48, line 52, or     -   direct dyes in the presence of cationic amphotere, substantive         polymer, as described in EP-953 334, especially on page 2, line         39 to page 7, line 44, with direct dyes as described on page 8,         line 54 to page 27, line 16, and polymers as described on page         27, line 17 to page 30, line 14, or     -   direct dyes formulations with polymer thickener on the basis of         acrylic acid, as described in EP-970 685, especially on page 2,         line 39 to page 10, line 1, with direct dyes as described on         page 10, line 7 to page 48, line 15, with polymers as described         on page 48, line 17 to page 49, line 28.     -   The colouring composition for carrying out the method according         to the invention in many cases comprises at least one         surfactant, there being suitable in principle anionic and also         zwitterionic, ampholytic, non-ionic and cationic surfactants. In         many cases, however, it has proved advantageous to select the         surfactants from anionic, zwitterionic and non-ionic         surfactants.     -   Anionic surfactants suitable for use in the colouring         compositions for carrying out the method according to the         invention include all anionic surface-active substances that are         suitable for use on the human body. Such substances are         characterised by an anionic group that imparts water solubility,         for example a carboxylate, sulfate, sulfonate or phosphate         group, and a lipophilic alkyl group having approximately from 10         to 22 carbon atoms. In addition, glycol or polyglycol ether         groups, ester, ether and amide groups and also hydroxy groups         may be present in the molecule. The following are examples of         suitable anionic surfactants, each in the form of sodium,         potassium or ammonium salts or mono-, di- or tri-alkanolammonium         salts having 2 or 3 carbon atoms in the alkanol group:     -   linear fatty acids having from 10 to 22 carbon atoms (soaps),     -   ether carboxylic acids of formula R—O—(CH₂—CH₂—O)_(x)—CH₂—COOH,         in which R is a linear alkyl group having from 10 to 22 carbon         atoms and x=0 or from 1 to 16,     -   acyl sarcosides having from 10 to 18 carbon atoms in the acyl         group,     -   acyl taurides having from 10 to 18 carbon atoms in the acyl         group,     -   acyl isothionates having from 10 to 18 carbon atoms in the acyl         group,     -   sulfosuccinic mono- and di-alkyl esters having from 8 to 18         carbon atoms in the alkyl group and sulfosuccinic         monoalkylpolyoxyethyl esters having from 8 to 18 carbon atoms in         the alkyl group and from 1 to 6 oxyethyl groups,     -   linear alkane sulfonates having from 12 to 18 carbon atoms,     -   linear α-olefin sulfonates having from 12 to 18 carbon atoms,     -   α-sulfo fatty acid methyl esters of fatty acids having from 12         to 18 carbon atoms,     -   alkyl sulfates and alkyl polyglycol ether sulfates of formula         R′—O(CH₂—CH₂—O)_(x)—SO₃H, in which R′ is a preferably linear         alkyl group having from 10 to 18 carbon atoms and x′=0 or from 1         to 12,     -   mixtures of surface-active hydroxysulfonates according to DE-A-3         725 030, especially page 3, lines 40 to 55,     -   sulfated hydroxyalkylpolyethylene and/or         hydroxyalkylenepropylene glycol ethers according to DE-A-3 723         354, especially page 4, lines 42 to 62,     -   sulfonates of unsaturated fatty acids having from 12 to 24         carbon atoms and from 1 to 6 double bonds according to DE-A-3         926 344, especially page 2, lines 36 to 54,     -   esters of tartaric acid and citric acid with alcohols which are         addition products of approximately from 2 to 15 molecules of         ethylene oxide and/or propylene oxide with fatty alcohols having         from 8 to 22 carbon atoms, or     -   anionic surfactants, as described in WO 00/10518, especially         page 45, line 11 to page 48, line 3.

Preferred anionic surfactants are alkyl sulfates, alkyl polyglycol ether sulfates and ether carboxylic acids having from 10 to 18 carbon atoms in the alkyl group and up to 12 glycol ether groups in the molecule, and also especially salts of saturated and especially unsaturated C₈-C₂₂carboxylic acids, such as oleic acid, stearic acid, isostearic acid and palmitic acid.

Surface-active compounds that carry at least one quaternary ammonium group and at least one —COO⁽⁻⁾ or —SO₃ ⁽⁻⁾ group in the molecule are termed zwitterionic surfactants. Zwitterionic surfactants that are especially suitable are the so-called betaines, such as the N-alkyl-N,N-dimethylammonium glycinates, for example cocoalkyldimethylammonium glycinate, N-acylaminopropyl-N,N-dimethylammonium glycinates, for example cocoacylaminopropyl-dimethylammonium glycinate, and 2-alkyl-3-carboxymethyl-3-hydroxyethylimidazolines having from 8 to 18 carbon atoms in the alkyl or acyl group and also cocoacylaminoethylhydroxyethylcarboxymethyl glycinate. A preferred zwitterionic surfactant is the fatty acid amide derivative known by the CTFA name cocoamidopropyl betaine.

Ampholytic surfactants are to be understood as meaning surface-active compounds that, in addition to a C₈-C₁₈-alkyl or -acyl group, contain at least one free amino group and at least one —COOH or —SO₃H group in the molecule and are capable of forming internal salts. Examples of suitable ampholytic surfactants include N-alkylglycines, N-alkylpropionic acids, N-alkylaminobutyric acids, N-alkyliminodipropionic acids, N-hydroxyethyl-N-alkylamidopropyl-glycines, N-alkyltaurines, N-alkylsarcosines, 2-alkylaminopropionic acids and alkylaminoacetic acids, each having approximately from 8 to 18 carbon atoms in the alkyl group. Ampholytic surfactants to which special preference is given are N-cocoalkyl-aminopropionate, cocoacylaminoethylaminopropionate and C₁₂-C₁₈acylsarcosine.

Non-ionic surfactants are described in WO 00/10519, especially page 45, line 11 to page 50, line 12.

Non-ionic surfactants contain as the hydrophilic group, for example, a polyol group, a polyalkylene glycol ether group or a combination of polyol and polyglycol ether groups.

Such compounds are, for example:

-   -   addition products of from 2 to 30 mol of ethylene oxide and/or         from 0 to 5 mol of propylene oxide with linear fatty alcohols         having from 8 to 22 carbon atoms, with fatty acids having from         12 to 22 carbon atoms and with alkylphenols having from 8 to 15         carbon atoms in the alkyl group,     -   C₁₂-C₂₂ fatty acid mono- and di-esters of addition products of         from 1 to 30 mol of ethylene oxide with glycerol,     -   C₈-C₂₂alkyl-mono- and -oligo-glycosides and ethoxylated         analogues thereof,     -   addition products of from 5 to 60 mol of ethylene oxide with         castor oil and hydrogenated castor oil,     -   addition products of ethylene oxide with sorbitan fatty acid         esters,     -   addition products of ethylene oxide with fatty acid         alkanolamides.

Examples of cationic surfactants that can be used in the colouring compositions for carrying out the method according to the invention are especially quaternary ammonium compounds. Preference is given to ammonium halides, such as alkyltrimethylammonium chlorides, dialkyldimethylammonium chlorides and trialkylmethylammonium chlorides, for example cetyltrimethylammonium chloride, stearyltrimethylammonium chloride, distearyldimethy-lammonium chloride, lauryldimethylammonium chloride, lauryldimethylbenzylammonium chloride and tricetylmethylammonium chloride. Further cationic surfactants that can be used in accordance with the invention are quaternised protein hydrolysates.

-   -   Also suitable in accordance with the invention are cationic         silicone oils, such as, for example, the commercially available         products Q2-7224 (manufacturer: Dow Corning; a stabilised         trimethylsilylamodimethicone), Dow Corning 929 emulsion         (comprising a hydroxylamino-modified silicone, which is also         referred to as amodimethicone), SM-2059 (manufacturer: General         Electric), SLM-55067 (manufacturer: Wacker) and also Abil®-Quat         3270 and 3272 (manufacturer: Th. Goldschmidt; diquaternary         polydimethylsiloxanes, quaternium-80), or silicones, as         described in WO 00/12057, especially page 45, line 9 to page 55,         line 2.

Alkylamidoamines, especially fatty acid amidoamines, such as the stearylamidopropyl-dimethylamine obtainable under the name Tego Amid® 18, are distinguished not only by a good conditioning action but also especially by their good biodegradability.

Quaternary ester compounds, so-called “esterquats”, such as the methyl hydroxyalkyl-dialkoyloxyalkylammonium methosulfates marketed under the trademark Stepantex®, are also very readily biodegradable.

An example of a quaternary sugar derivative that can be used as cationic surfactant is the commercial product Glucquat®100, according to CTFA nomenclature a “lauryl methyl gluceth-10 hydroxypropyl dimonium chloride”.

The alkyl-group-containing compounds used as surfactants may be single substances, but the use of natural raw materials of vegetable or animal origin is generally preferred in the preparation of such substances, with the result that the substance mixtures obtained have different alkyl chain lengths according to the particular starting material used.

The surfactants that are addition products of ethylene and/or propylene oxide with fatty alcohols or derivatives of such addition products may either be products having a “normal” homologue distribution or products having a restricted homologue distribution. “Normal” homologue distribution is to be understood as meaning mixtures of homologues obtained in the reaction of fatty alcohol and alkylene oxide using alkali metals, alkali metal hydroxides or alkali metal alcoholates as catalysts. Restricted homologue distributions, on the other hand, are obtained when, for example, hydrotalcites, alkali metal salts of ether carboxylic acids, alkali metal oxides, hydroxides or alcoholates are used as catalysts. The use of products having restricted homologue distribution may be preferred.

Further preferred active ingredients, adjuvants and additives are as follows:

-   -   non-ionic polymers, for example vinylpyrrolidone/vinyl acrylate         copolymers, polyvinyl-pyrrolidone and vinylpyrrolidone/vinyl         acetate copolymers and polysiloxanes,     -   cationic polymers, such as quaternised cellulose ethers,         polysiloxanes having quaternary groups, dimethyldiallylammonium         chloride polymers, copolymers of dimethyldiallyl-ammonium         chloride and acrylic acid, as available commercially under the         name Merquat® 280 and the use of which in hair colouring is         described, for example, in DE-A-4 421 031, especially page 2,         lines 20 to 49, or EP-A-953 334, especially page 27, line 17 to         page 30, line 11, acrylamide/dimethyldiallylammonium chloride         copolymers, diethyl-sulfate-quaternised dimethylaminoethyl         methacrylate/vinylpyrrolidone copolymers,         vinylpyrrolidone/imidazolinium methochloride copolymers,     -   quaternised polyvinyl alcohol,     -   zwitterionic and amphoteric polymers, such as, for example,         acrylamido-propyl-trimethylammonium chloride/acrylate copolymers         and octylacrylamide/methyl methacrylate/tert-butylaminoethyl         methacrylate/2-hydroxypropyl methacrylate copolymers,     -   anionic polymers, such as, for example, polyacrylic acids,         crosslinked polyacrylic acids, vinyl acetate/crotonic acid         copolymers, vinylpyrrolidone/vinyl acrylate copolymers, vinyl         acetate/butyl maleate/isobornyl acrylate copolymers, methyl         vinyl ether/maleic anhydride copolymers and acrylic acid/ethyl         acrylate/N-tert-butyl acrylamide terpolymers,     -   thickeners, such as agar, guar gum, alginates, xanthan gum, gum         arabic, karaya gum, locust bean flour, linseed gums, dextrans,         cellulose derivatives, e.g. methyl cellulose, hydroxyalkyl         cellulose and carboxymethyl cellulose, starch fractions and         derivatives, such amylose, amylopectin and dextrins, clays, e.g.         bentonite or fully synthetic hydrocolloids such as, for example,         polyvinyl alcohol,     -   structuring agents, such as glucose and maleic acid,     -   hair-conditioning compounds, such as phospholipids, for example         soya lecithin, egg lecithin, and cephalins, silicone oils, and         also conditioning compounds, for example such as those described         in DE-A-19 729 080, especially page 2, lines 20 to 49, EP-A-834         303, especially page 2, line 18 to page 3, line 2, or EP-A-312         343, especially page 2, line 59 to page 3, line 11,     -   protein hydrolysates, especially elastin, collagen, keratin,         milk protein, soya protein and wheat protein hydrolysates,         condensation products thereof with fatty acids and also         quaternised protein hydrolysates,     -   perfume oils, dimethyl isosorbitol and cyclodextrins,     -   solubilisers, such as ethanol, isopropanol, ethylene glycol,         propylene glycol, glycerol and diethylene glycol,     -   anti-dandruff active ingredients, such as piroctones, olamines         and zinc Omadine,     -   further substances for adjusting the pH value,     -   active ingredients such as panthenol, pantothenic acid,         allantoin, pyrrolidonecarboxylic acids and salts thereof, plant         extracts and vitamins,     -   cholesterol,     -   light stabilisers and UV absorbers, as described, for example,         in EP-A-819 422, especially page 4, lines 34 to 37,     -   consistency regulators, such as sugar esters, polyol esters or         polyol alkyl ethers,     -   fats and waxes, such as spermaceti, beeswax, montan wax,         paraffins, fatty alcohols and fatty acid esters,     -   fatty alkanolamides,     -   polyethylene glycols and polypropylene glycols having a         molecular weight of from 150 to 50 000, for example such as         those described in EP-A-801 942, especially page 3, lines 44 to         55,     -   complexing agents, such as EDTA, NTA and phosphonic acids,     -   swelling and penetration substances, such as polyols and polyol         ethers, as listed extensively, for example, in EP-A-962 219,         especially page 27, lines 18 to 38, for example glycerol,         propylene glycol, propylene glycol monoethyl ether, butyl         glycol, benzyl alcohol, carbonates, hydrogen carbonates,         guanidines, ureas and also primary, secondary and tertiary         phosphates, imidazoles, tannins, pyrrole,     -   opacifiers, such as latex,     -   pearlising agents, such as ethylene glycol mono- and         di-stearate,     -   propellants, such as propane-butane mixtures, N₂O, dimethyl         ether, CO₂ and air, and also     -   antioxidants,     -   polyols or polyethers, as described in EP-A-962 219, especially         page 27, lines 14 to 38,     -   thickening polymers, as described in EP-A-970 684, especially         page 48, line 16 to page 51, line 4,     -   sugar-containing polymers, as described in EP-A-970 687,         especially page 28, line 17 to page 29, line 23,     -   quaternary ammonium salts, as described in WO 00/10517,         especially page 44, line 16 to page 46, line 23.

In the context of the present invention, oxidizing agents are understood to be any oxidizing agent customarily used for oxidative hair colouring, for example dilute hydrogen peroxide solutions, hydrogen peroxide emulsions or hydrogen peroxide gels, alkaline earth metal peroxides, organic peroxides, such as urea peroxides, melamine peroxides, or alkalimetalbromat fixations are also applicable if a shading powder on the basis of semi-permanent, direct hair dyes is used.

Preferred oxidizing agent is hydrogen peroxide, preferred in about 2 to 30% by weight, more preferred in 3 to 20% by weight, and most preferred in 6 to 12% by weight of the total weight of a watery composition such as a solution, dispersion, a gel or emulsion.

The watery composition can comprise all customary components, which are used for the different applications of oxidizing agent compositions as described in K. Schrader, “Grundlagen und Rezepturen der Kosmetika”, 2. Aufl. (1989), page 832-840.

Further preferred oxidizing agents are

-   -   oxidizing agents to achieve lightened colouration, as described         in WO 97/20545, especially page 9, lines 5 to 9,     -   oxidizing agents in the form of permanent-wave fixing solution,         as described in DE-A-19 713 698, especially page 4, lines 52 to         55, and lines 60 and 61 or EP-A-1 062 940, especially page 6,         lines 41 to 47, (and in the equivalent WO 99/40895).

An oxidizing agents may be present in the colouring compositions for carrying out the method according to the invention preferably in an amount of from 0.01% to 6%, especially from 0.01% to 1%, based on the total dyeing composition. Preferred catalysts are metal ions, such as for example Zn²⁺, Cu²⁺, Fe²⁺, Fe³⁺, Mn²⁺, Mn⁴⁺, Li⁺, Mg²⁺, Ca²⁺ and Al³⁺, preferably Zn²⁺, Cu²⁺ and Mn²⁺.

The metal ions are applicable in any physiological suitable salts form. Preferred salts are acetate, sulfate, halogenide, lactate and tartrate.

Alkalimetalsulfits, such as sodium-, potassium-, lithium-sulfite, Alkalimetaldisulfits, such as sodium-, potassium-, lithium-disulfite, ascorbic acid, tert.-Butylhydrochinon and Ammoniumthiolactat.

In general, the coloration with an oxidative agent is conducted in the presence of a base. Bases are for example ammonia, alkali metal carbonates, earth metal carbonates, alkanol amines, such as for example mono-, di- or triethanolamine, alkali metal hydroxides, earth metal hydroxides, compounds of the formula

wherein,

-   R is a propyl residue, which substituted with OH or C₁-C₄-alkyl, -   R₃, R₄, R₅ and R₆ are independently or dependently from each other     hydrogen, C₁-C₄-alkyl or hydroxy-(C₁-C₄)-alkyl.

Alkali metal is for example sodium, potassium or lithium.

Earth metal is for example magnesium or calcium.

Acids are inorganic or organic acids, such as hydrochloride, tartrat acid, citric acid, ascorbic acid and phosphor acid.

The use of UV absorbers can effectively protect natural and dyed hair from the damaging rays of the sun and increase the wash fastness of dyed hair.

Preferred UV absorbers the colouring compositions for carrying out the method according to the invention are:

-   -   cationic benzotriazole UV absorbers as for example described in         WO 01/36396 especially on page 1, line 20 to page 2, line 24,         and preferred on page 3 to 5, and on pages 26 to 37, or     -   cationic benzotriazole UV in combination with antioxidants as         described in WO 01/36396, especially on page 11, line 14 to page         18, or     -   UV absorbers in combination with antioxidants as described in         U.S. Pat. No. 5,922,310, especially in column 2, lines 1 to 3,     -   UV absorbers in combination with antioxidants as described in         U.S. Pat. No. 4,786,493, especially in column 1, 42 to column 2,         line 7, and preferred in column 3, 43 to column 5, line 20, or     -   combination of UV absorbers as described in U.S. Pat. No.         5,830,441, especially in column 4, lines 53 to 56, or     -   combination of UV absorbers as described in WO 01/36396,         especially on page 11, lines 9 to 13, or     -   triazine derivatives provide effective UV protection as         described in WO 98/22447, especially on page 1, line 23 to page         2, line 4, and preferred on page 2, line 11 to page 3, line 15         and most preferred on pages 6 to 7, and 12 to 16, or

combination of the cosmetic formulations as described in WO 98/22447 with one or more than one further UV filter as described in the following patents: EP 895776 Comp. in Rows 48-58, p 3; R 25 + 33, p 5 WO 9220690 Polymeric comp in Examples 3-6 EP 1000950 Comp. in Table 1, pp 18-21 EP 1060734 T 1-3, pp 11-14 EP 1059082 Ex 1; T 1, pp 9-11 EP 1008586 Ex 1-3, pp 13-15 EP 1005855 T 3, p 13 EP 1129695 Ex 1-7, pp 13-14 EP 967200 Ex 2; T 3-5, pp 17-20 EP 945125 T 3 a + b, pp 14-15 EP 924246 T 2, p 9 EP 911020 T 2, p 11-12 EP 916335 T 2-4, pp 19-41 EP 852137 T 2, pp 41-46 EP 858318 T 1, p 6 EP 826361 T 1, pp 5-6 EP 503338 T 1, pp 9-10 WO 9301164 T 1 + 2, pp 13-22 EP 823418 Ex 1-4, pp 7-8 WO 9714680 Ex 1-3, p 10 EP 1027883 Compound VII, p 3 EP 832641 Ex 5 + 6 p 7; t 2, p 8 US 5338539 Ex 1-9, pp 3 + 4 EP 517103 Ex 3, 4, 9, 10 pp 6-7 EP 1123934 T 3, p 10 EP 1027883 Comp I-VI, p 3 EP 969004 Ex 5, T 1, pp 6-8 US 5801244 Ex 1-5, pp 6-7 EP 832642 Ex 22, T 3 pp, 10-15; T 4, p 16 US 5346691 (EP 570838) Ex 40, p 7; T 5, p 8 EP 517104 Ex 1, T 1, pp 4-5; Ex 8, T 2, pp 6-8 WO 200149686 Ex 1-5, pp 16-21 EP 944624 Ex 1 + 2, pp 13-15 EP 933376 Ex 1-15, pp 10-21 EP 863145 Ex 1-11, pp 12-18 EP 780382 Ex 1-11, pp 5-7 EP 626950 all examples EP 1081140 Ex 1-9, pp 11-16 WO 9217461 Ex 1-22, pp 10-20 WO 0168047 Tables on pp 85-96 EP 613893 Ex 1-5 + 15, T 1, pp 6-8 EP 1064922 Compounds 1-34, pp 6-14 EP 1028120 Ex 1-5, pp 5-13 EP 1008593 Ex 1-8, pp 4-5 EP 669323 Ex 1-3, p 5 EP 1108712 4,5-Dimorpholino-3-hydroxypyridazine JP 2000319629 CAS Regno. 80142-49-0, 137215-83-9, 307947-82-6 EP 420707 B1 Ex 3, p 13 (80142-49-0) US 5635343 all examples EP 1167358 all examples (Abbreviations T: table, R: row, Comp: compound, Ex: compound(s) of patent example, p = page; pp = pages) In addition to the triazine UV absorbers described in WO 98/22447, the cosmetic formulations can also contain one or more than one further UV protective of the following substance classes:

-   -   p-aminobenzoic acid derivatives, for example         4-dimethylaminobenzoic acid 2-ethylhexyl ester;     -   salicylic acid derivatives, for example salicylic acid         2-ethylhexyl ester;     -   benzophenone derivatives, for example         2-hydroxy-4-methoxybenzophenone and its 5-sulfonic acid         derivative;     -   dibenzoylmethane derivatives, for example         1-(4-tert-butylphenyl)-3-(4-methoxyphenyl)-propane-1,3-dione;     -   diphenylacrylates, for example 2-ethylhexyl         2-cyano-3,3-diphenylacrylate, and 3-(benzofuranyl)         2-cyanoacrylate;     -   3-imidazol-4-ylacrylic acid and esters;     -   benzofuran derivatives, especially 2-(p-aminophenyl)benzofuran         derivatives, described in EP-A-582 189, US-A-5 338 539, US-A-5         518 713 and EP-A-613 893;     -   polymeric UV absorbers, for example the benzylidene malonate         derivatives described in EP-A-709 080;     -   cinnamic acid derivatives, for example the 4-methoxycinnamic         acid 2-ethylhexyl ester and isoamyl ester or cinnamic acid         derivatives described in US-A-5 601 811 and WO 97/00851;     -   camphor derivatives, for example         3-(4′-methyl)benzylidene-bornan-2-one,         3-benzyl-idenebornan-2-one, N-[2(and         4)-2-oxyborn-3-ylidene-methyl)-benzyl]acrylamide polymer,         3-(4′-trimethylammonium)-benzylidene-bornan-2-one methyl         sulfate,         3,3′-(1,4-phenylenedimethine)-bis(7,7-dimethyl-2-oxo-bicyclo[2.2.1         ]heptane-1-methanesulfonic acid) and salts,         3-(4′-sulfo)benzylidene-bornan-2-one and salts;         camphorbenzalkonium methosulfate;     -   hydroxyphenyltriazine compounds, for example         2-(4′-methoxyphenyl)-4,6-bis(2′-hydroxy-4′-n-octyloxyphenyl)-1,3,5-triazine;         2,4-bis{[4-(3-(2-propyloxy)-2-hydroxy-propyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;         2,4-bis{[4-(2-ethyl-hexyloxy)-2-hydroxy]-phenyl}-6-[4-(2-methoxyethyl-carboxyl)-phenylamino]-1,3,5-triazine;         2,4-bis{[4-(tris(trimethylsilyloxy-silylpropyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;         2,4-bis{[4-(2″-methylpropenyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;         2,4-bis{([4-(1′,1′,1′,3′,5′,5′,5′-heptamethyltrisilyl-2″-methyl-propyloxy)-2-hydroxy]-phenyl}-6-(4-methoxyphenyl)-1,3,5-triazine;         2,4-bis{[4-(3-(2-propyloxy)-2-hydroxy-propyloxy)-2-hydroxy]-phenyl}-6-[4-ethylcarboxy)-phenylamino]-1,3,5-triazine;     -   benzotriazole compounds, for example         2,2′-methylene-bis(6-(2H-benzotriazol-2-yl)-4-(1,1,3,3-tetramethylbutyl)-phenol;     -   trianilino-s-triazine derivatives, for example         2,4,6-trianiline-(p-carbo-2′-ethyl-1′-oxy)-1,3,5-triazine and         the UV absorbers disclosed in U.S. Pat. No. 5,332,568, EP-A-517         104, EP-A-507 691, WO 93/17002 and EP-A-570 838;     -   2-phenylbenzimidazole-5-sulfonic acid and salts thereof;     -   methyl o-aminobenzoates;     -   physical sunscreens coated or not as titanium dioxide, zinc         oxide, iron oxides, mica, MnO, Fe₂O₃, Ce₂O₃, Al₂O₃, ZrO₂.         (surface coatings: polymethylmethacrylate, methicone         (methylhydrogenpolysiloxane CAS 9004-73-3), dimethicone,         isopropyl titanium triisostearate (CAS 61417-49-0), metal soaps         as magnesium stearate (CAS 4086-70-8), perfluoroalcohol         phosphate as C9-15 fluoroalcohol phosphate (CAS 74499-44-8; JP         5-86984, JP 4-330007)). The primary particle size is an average         of 15 nm-35 nm and the particle size in dispersion is in the         range of 100 nm-300 nm.     -   aminohydroxy-benzophenone derivatives disclosed in DE 10011317,         EP 1133980 and EP 1046391     -   phenyl-benzimidazole derivatives as disclosed in EP 1167358     -   The UV absorbers described in “Sunscreens”, Eds. N. J.         Lowe, N. A. Shaath, Marcel Dekker, Inc., New York and Basle or         in Cosmetics & Toiletries (107), 50ff (1992) also can be used as         additional UV protective substances.

Synergistic effects are observed when UV absorbers are used in combination with antioxidants. Examples of antioxidants that can be used are listened in WO 01/36396 (pages 11-18), U.S. Pat. No. 5,922,310 and U.S. Pat. No. 4,786,493.

Further preferred UV absorbers used in addition to the uncharged and cationic benzotriazole UV absorbers in the formulations without limitation to those listed in the following might be benzophenone-type substances such as benzophenone-1, benzophenone-2, benzophenone-3, benzophenone-4, benzophenone-5 (sodium salt) or benzotriazol-type substances such as benzenesulfonic acid, 3-(2H-benzotriazol-2-yl)-4-hydroxy-5-(1-methylpropyl)-, monosodium salt; 2-(5-chloro-2H-benzotriazol-2-yl)-6-(1,1-dimethylethyl)-4-methyl-phenol; 2-(2H-benzotriazol-2-yl)-6-dodecyl-4-methyl-phenol, branched and linear. Typical ingredients in the oil phase of emulsions (water in oil, oil in water or triple emulsion) or used in hair oils can be chosen from the following substance groups without limiting the kind of lipophilic ingredients to those substances:

Suitable cosmetic preparations may contain usually from 0.05 to 40% by weight, preferably from 0.1 to 20% by weight, based on the total weight of the composition, of one or more UV absorbers.

Preferred are the cosmetic preparations contain at least one triazine derivative UV absorber, for example, from 0.1 to 40% by weight, preferably from 0.1 to 20% by weight and especially from 0.5 to 10% by weight, based on the total weight of the composition, and the cosmetic preparations contain at least one cationic benzotriazole from 0.05-20% by weight, preferred from 0.1-20% by weight, based on the total weight of the composition. Typical cosmetic formulations containing uncharged and/or cationic benzotriazoles and/or antioxidants alone or in combinations are rinse-off products (e.g. shampoos, hair rinses, conditioners etc.),

Suitable cosmetic formulations are:

-   -   cosmetic hair-treatment preparations, e.g. hair-washing         preparations in the form of shampoos and conditioners, hair-care         preparations, e.g. pre-treatment preparations or leave-on         products such as sprays, creams, gels, lotions, mousses and         oils, or hair tonics, styling creams, styling gels, pomades,         hair rinses, treatment packs, intensive hair treatments,         hair-structuring preparations, e.g. hair-waving preparations for         permanent waves (hot wave, mild wave, cold wave),         hair-straightening preparations, liquid hair-setting         preparations, hair foams, hairsprays, bleaching preparations,         e.g. hydrogen peroxide solutions, lightening shampoos, bleaching         creams, bleaching powders, bleaching pastes or oils, temporary,         semi-permanent or permanent hair colourants, preparations         containing self-oxidising dyes, or natural hair colourants, such         as henna or camomile.

The final formulations listed may exist in a wide variety of presentation forms, for example:

-   -   in the form of liquid preparations as a W/O, O/W, O/W/O, W/O/W         or PIT emulsion and all kinds of microemulsions,     -   in the form of a gel,     -   in the form of an oil, a cream, milk or lotion,     -   in the form of a powder, a lacquer, a tablet or make-up,     -   in the form of a stick,     -   in the form of a spray (spray with propellant gas or pump-action         spray) or an aerosol,     -   in the form of a foam, or     -   in the form of a paste.

Of special importance as cosmetic preparations for the hair are the above-mentioned preparations for hair treatment, especially hair-washing preparations in the form of shampoos, hair conditioners, hair-care preparations, e.g. pre-treatment preparations, hair tonics, styling creams, styling gels, pomades, hair rinses, treatment packs, intensive hair treatments, hair-straightening preparations, liquid hair-setting preparations, hair foams and hairsprays. Of special interest are hair-washing preparations in the form of shampoos.

A shampoo has, for example, the following composition: from 0.01 to 5% by weight of a UV absorber according to the invention, 12.0% by weight of sodium laureth-2-sulfate, 4.0% by weight of cocoamidopropyl betaine, 3.0% by weight of sodium chloride, and water ad 100%.

Any known method suitable for the preparation of microparticles can be used for the preparation of the micronised UV absorbers, for example:

-   -   wet-grinding with a hard grinding medium, for example zirconium         silicate and a protective surfactant or a protective polymer in         water or in a suitable organic solvent;     -   spray-drying from a suitable solvent, for example aqueous         suspensions or suspensions containing organic solvents, or true         solutions in water, ethanol, dichloroethane, toluene or         N-methylpyrrolidone etc.;     -   by the expansion according to the RESS method (Rapid Expansion         of Supercritical Solutions) of supercritical fluids (e.g. CO₂)         in which the UV filter or filters is/are dissolved, or the         expansion of fluid carbon dioxide together with a solution of         one or more UV filters in a suitable organic solvent;     -   by reprecipitation from suitable solvents, including         supercritical fluids (GASR method=Gas Anti-Solvent         Recrystallisation/PCA method=Precipitation with Compressed         Anti-solvents).

As grinding apparatus for the preparation of the micronised organic UV absorbers there may be used, for example, a jet mill, ball mill, vibratory mill or hammer mill, preferably a high-speed mixing mill. The grinding is preferably carried out with a grinding aid, for example an alkylated vinylpyrrolidone polymer, a vinylpyrrolidone/vinyl acetate copolymer, an acyl glutamate, an alkyl polyglucoside, ceteareth-25 or a phospholipid. The micronised UV absorbers so obtained usually have an average particle size that is from 0.02 to 2 μm, preferably from 0.05 to 1.5 μm, and more especially from 0.1 to 1.0 μm.

The UV absorbers can also be used dry in powder form. For that purpose the UV absorbers are subjected to known grinding methods, such as vacuum atomization, countercurrent spray-drying etc. Such powders have a particle size of from 0.1 μm to 2 μm. To avoid the occurrence of agglomeration, the UV absorbers can be coated with a surface-active compound prior to the pulverisation method, for example with an anionic, non-ionic or amphoteric surfactant, e.g. a phospholipid or a known polymer, such as PVP, or an acrylate. The colouring compositions for carrying out the method according to the invention may further comprise antimicrobial agents.

Typical antimicrobial preservatives and antimicrobial actives used in formulations (in most cases the INCI name of the antimicrobial substances is mentioned): formaldehyde and paraformaldehyde, hydroxy biphenyls and its salts such as ortho-phenylphenol, zinc pyrithion, chlorobutanol, hydroxy benzoic acids and their salts and esters such as methyl paraben, ethyl paraben, propyl paraben, butyl paraben, dibromo hexamidine and its salts including isothionate (4,4′-hexamethylenedioxy-bis(3-bromo-benzamidine) and 4,4′-hexamethylenedioxy-bis(3-bromo-benzamidinium 2-hydroxyethanesulfonate), mercury, (aceto-O)phenyl (especially phenyl mercuric acetate) and Mercurate(2-),(orthoborate(3-)-O)phenyl, dihydrogene (especially phenyl mercuric borate), 1,3-bis(2-ethylhexyl)-hexahydro-5-methyl-5-pyrimidine (Hexetidin), 5-bromo-5-nitro-1,3-dioxan, 2-bromo-2-nitro-1,3-propandiol, 2,4-dichlorobenzyl alcohol, 3,4,4′ trichlorocarbanilide (Trichlorcarban), p-chloro-m-cresol, 2,4,4′-trichloro 2-hydroxy diphenylether (triclosan), 4,4′-dichloro 2-hydroxy diphenylether, 4-chloro-3,5-dimethylphenol (Chloroxylenol), imidazolidinyl urea, poly-(hexamethylene biguanide) hydrochloride, 2-phenoxy ethanol (phenoxyethanol), hexamethylene tetramine (Methenamine), 1-(3-chloroallyl)-3,5,7-triaza-1-azonia-adamantanchloride (Quaternium 15), 1-(4-chlorophenyoxy)-1-(1-imidazolyl)3,3-dimethyl-2-butanone (Climbazole), 1,3-bis(hydroxymethyl)-5,5-dimethyl-2,4-imidazolidinedione (DMDM hydantoin), benzyl alcohol, 1,2-dibromo-2,4-dicyano butane, 2,2′ methylene-bis(6-bromo-4-chloro phenol) (bromochlorophene), methylchloroisothiazolone, methylisothiazolone, octylisothiazolone, benzylisothiazolone, 2-benzyl-4-chlorophenol (Chlorophenone), chloracetamide, chlorhexidine, chlorhexidine acetate, chlorhexidine gluconate, chlorhexidine hydrochloride, 1-phenoxy-propane-2-ol (phenoxyisopropanol), 4,4-dimethyl-1,3-oxazolidine (dimethyl oxazolidine), diazolidinyl urea, 4,4′-hexamethylenedioxybisbenzamidine and 4,4′-hexamethylenedioxybis(benzamidinium-2-hydroxyethanesulfonate), glutaraldehyde (1,5-pentanedial), 7-ethylbicyclooxazolidine, 3-(4-chlorophenoxy)-1,2-propandiol (chlorophenesin), phenylmethoxymethanol and ((phenylmethoxy)methoxy)-methanol (benzylhemiformal), N-alkyl(C12-C22)trimethyl ammoniumbromide and -chloride (cetrimonium bromide, cetrimonium chloride), benzyl-dimethyl-(4-(2-(4-(1,1,3,3-tetramethylbutyl)-phenoxy)-ethoxy)-ethyl)-ammoniumchloride (benzethonium chloride), Alkyl-(C8-C18)-dimethyl-benzylammonium chloride, -bromide and saccharinate (benzalkonium chloride, benzalkonium bromide, benzalkonium saccharinate), benzoic acid and its salts and esters, propionic acid and its salts, salicylic acid and its salt, sorbic acid and its salts, sodium iodiate, inorganic sulfites and bisulfites such as sodium sulfite, dehydroacetic acid, formic acid, mercurate(1-ethyl)2-mercaptobenzoate(2-)-O,S-,hydrogene (Thiomersal or Thiomerosal), 10-undecylenic acid and its salts, octopirox (piroctone olamine), sodium hydroxy methyl-aminoacetate (sodium hydroxymethylglycinate), 3-iodo-2-propynyl butylcarbamate, 10-undecylenic acid, sulfur.

Combinations with natural antimicrobials or chemically modified natural substances with antimicrobial activities such as chitosans and chitosan derivatives, farnesol, plant extracts such as clove oil, blue cypres oil etc. can be also used.

For use on human hair, the dyeing compositions can usually be incorporated into an aqueous cosmetic carrier. Suitable aqueous cosmetic carriers include, for example, creams, sprays, emulsions, gels, powders and also surfactant-containing foaming solutions, e.g. shampoos or other preparations, that are suitable for use on keratin-containing fibers. Such forms of use are described in detail in Research Disclosure 42448 (August 1999). If necessary, it is also possible to incorporate the dyeing compositions into anhydrous carriers, as described, for example, in U.S. Pat. No. 3,369,970, especially column 1, line 70 to column 3, line 55. The dyeing compositions according to the invention are also excellently suitable for the colouring method described in DE-A-3 829 870 using a colouring comb or a colouring brush.

Further carriers for dying compositions are for example described in “Dermatology”, edited by Ch. Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7, Ch. Zviak, The Science of Hair Care, chapter 7, pages 248-250, especially on page 243, line 1 to page 244, line 12.

Suitable formulations of cationic dyes, which can be used in the colouring compositions for carrying out the method according to the invention are described for example in

-   -   in WO 95/01772, especially on page 11, line 29 to page 12, line         7, or     -   in WO 01/66646, especially on page 7, line 1 to page 22, and         preferred from page 16, line 20 to page 22, or     -   direct dyes as described in DE-A-19 713 698, especially page 3,         line 51 to page 4, line 29 and page 4, line 65 to page 5, line         60, or     -   direct dyes and oxidizing agent as described in WO 97/20545,         especially on page 9, line 1 to page 11, line 4, in particular         on page 11, line 6 to page 13, line 19.

Preferred formulations of cationic dyes with other dyes, which can be used in the colouring compositions for carrying out the method according to the invention, are:

-   -   combinations of Pyrazolo-[1,5-a]-pyrimidines with at least one         cationic dye as described in EP 998,908, especially on page 47,         line 3 to page 49, line 26, and preferred on page 51, line 4 to         page 52, line 5, or     -   combinations of cationic dyes as described in FR-2788432,         especially on page 53, line 1 to page 63, line 23, especially a         combination of cationic dyes with Arianors in FR-2788432,         especially on pages 51 to 52, or especially a combination with         at least one Basic Brown 17, Basic brown 16, Basic Red 76 and         Basic Red 118, and/or at least one Basic Yellow 57, and/or at         least one Basic Blue 99, or     -   combinations of direct dyes and/or an oxidation dye and         oxidizing agents in the form of permanent-wave fixing solution,         especially with direct dyes as described in DE-A-19 713 698,         especially page 4, line 65 to page 35, line 59, or     -   combinations of cationic dyes and an oxidation dye of the         developer compound type and oxidizing agents as described in EP         850 638, especially on page 2, lines 3 to 12 and line 30 to page         14, and page 28, line 35 to page 30, line 20, preferred on page         30, line 25 to page 32, line 30, or     -   ready-to-use dyeing compositions and multicompartment device for         dyeing keratin fibers comprising combinations of an         extemporaneous mixture of a composition (A) containing one or         more oxidation dye precursors and optionally one or more         couplers, and of a composition (B), in powder form, containing         one or more direct dye, preferably cationic, optionally         dispersed in an organic pulverulent excipient and/or a mineral         pulverulent excipient, and a composition (C) containing one or         more oxidizing agent as described in U.S. Pat. No. 6,190,421,         especially in column 2, line 20 to line 31 in column 7, line 15         to column 8, line 43, and preferably in column 8, line 55 to         column 9, line 56, and preferably with direct dyes as described         in column 5, line 30 to column 7, line 14, or     -   a ready-to-use composition comprising, at least one oxidation         base, at least one cationic direct dye and at least one enzyme         of 2-electron oxidoreductase type in the presence of at least         one donor for the said enzyme as described in U.S. Pat. No.         6,228,129, especially in column 2, line 16 to column 25, line         55, and a multi-compartment dyeing device as described in column         26, lines 13 to 24, especially in column 26, line 26 to column         27, line 9, or     -   a ready-to-use composition comprising compositions of at least         one direct cationic dye and at least one nitrated benzene dye as         described in WO 99/20235 especially on page 1, line 25 to page         8, line 5, and on page 30, line 17 to page 34 line 25, with         cationic direct dyes as described on page 8, line 12 to page 25         line 6, and a multi-compartment dyeing device as described on         page 35, lines 21 to 27, especially on page 36, line 1 to page         37, or     -   a ready-to-use composition or a multi-compartment dyeing device         comprising compositions of at least one direct cationic dye and         at least one autooxidisable oxidation dye, especially benzene,         indol and indoline derivatives as described in WO 99/20234,         especially on page 26, line 5 to page 32, line 18, or     -   oxidation dyeing compositions of at least one direct dye and at         least one meta-Aminophenol derivative and at least one developer         compound and an oxidizing agent as described in EP 850 636,         especially on page 18, line 1 to page 22, line 11, or     -   oxidation dyeing compositions of at least one direct dye and at         least one developer compound selected from the group of         para-Phenylenediamine derivatives and Bis-Phenylalkylenediamine         and, and at least one coupler compound selected from the group         of meta-Diphenols and an oxidizing agent, as described in         EP-A-850 637, especially on page 19, line 24 to page 22, line         57,     -   cationic dye and e.g. a pyrazolo-(1,5-a)-pyrimidine derivatives,         as described in EP 998 908, especially on page 47, line 25 to         page 50, line 29, or     -   oxidative dye precursors (unsaturated aldehyde and coupler         compounds), as described in German Patent Application 197 172         24, especially on page 3, line 36 to page 9 line 64.

Cationic dyes may be present in the colouring compositions for carrying out the method according to the invention preferably in an amount of from 0.001% to 5%, especially from 0.01% to 1%, based on the total dyeing composition.

The pH value of the ready-to-use dyeing preparations is usually from 2 to 11, preferably from 5to 10.

The constituents of the aqueous carrier are used in the colouring compositions for carrying out the method according to the invention in the amounts customary for that purpose; for example emulsifiers may be used in concentrations of from 0.5 to 30% by weight and thickeners in concentrations of from 0.1 to 25% by weight of the total dyeing composition.

If direct dyes are used together with oxidation dyes and/or the addition salts thereof with an acid, they may be stored separately or together.

It is preferred to store the oxidation dyes and direct dyes, which are not stable to reduction, separately.

They may be stored in a liquid to paste-like preparation (aqueous or non-aqueous) or in the form of a dry powder.

When the dyes and adjuvants are stored together in a liquid preparation, the preparation should be substantially anhydrous in order to reduce reaction of the compounds.

When they are stored separately, the reactive components are intimately mixed with one another only immediately before use. In the case of dry storage, before use a defined amount of hot (from 50 to 80° C.) water is usually added and a homogeneous mixture prepared.

One preferred method of applying dyes containing formulations on hair is by using a multi-compartment dyeing device or “kit” or any other multi-compartment packaging system, as described for example in WO 97/20545 on page 4, line 19 to line 27.

The colouring compositions for carrying out the method according to the invention may combined with a suitable ready-to-use composition for the oxidation dyeing of keratin fibers, in particular human keratin, comprising an oxidizing agent, at least one direct dye and at least one oxidation dye precursor, as described in U.S. Pat. No. 6,190,421, in column 1, line 65 to column 3, line 65, especially in column 10, line 62 to column 12, line 65.

Preferably, such a ready-to-use composition is prepared according to a first preferred embodiment by a method which comprises a preliminary step which involves separately storing, on the one hand, a composition (A) comprising, in a medium which is suitable for dyeing, at least one developer compound, especially selected from para-phenylenediamines and bis(phenyl)alkylenediamines, and the acid-addition salts thereof, at least one coupler, especially selected from meta-phenylenediamines and the acid-addition salts thereof, and at least one cationic direct dye, on the other hand, a composition (B) containing, in a medium which is suitable for dyeing, at least one oxidizing agent and mixing them together at the time of use before applying this mixture to the keratin fibers.

According to a second preferred embodiment for the preparation of the ready-to-use dye composition, the method includes a preliminary step which involves separately storing, on the one hand, a composition (A) comprising, in a medium which is suitable for dyeing, at least one developer compound, especially selected from para-phenylenediamines and bis(phenyl)alkylenediamines, and the acid-addition salts thereof, at least one coupler compound, especially selected from meta-phenylenediamines and the acid-addition salts thereof; on the other hand, a composition (A′) comprising, in a medium which is suitable for dyeing, at least one cationic direct dye and, lastly, a composition (B) containing, in a medium which is suitable for dyeing, at least one oxidizing agent as defined above, and mixing them together at the time of use before applying this mixture to the keratin fibers.

The composition (A′) used according to this second variant of the method in accordance with the invention can optionally be in powder form, the cationic direct dye(s) in accordance with the invention itself (themselves) constituting, in this case, all of the said composition (A′) or optionally being dispersed in an organic and/or inorganic pulverulent excipient.

When it is present in the composition A′, the organic excipient can be of synthetic or plant origin and is selected in particular from crosslinked and non-crosslinked synthetic polymers, polysaccharides such as celluloses and modified or unmodified starches, as well as natural products containing them such as sawdust and plant gums (guar gum, carob gum, xanthan gum, etc.).

When it is present in the composition (A′), the inorganic excipient can contain metal oxides such as titanium oxides, aluminium oxides, kaolin, talc, silicates, mica and silicas.

A very suitable excipient in the colouring compositions for carrying out the method according to the invention is sawdust.

The powdered composition (A′) can also contain binders or coating products in an amount which preferably does not exceed approximately 3% by weight relative to the total weight of the said composition (A′).

These binders are preferably selected from oils and liquid fatty substances of inorganic, synthetic, animal or plant origin.

The composition (A′) may optionally also contain other adjuvants, in powdered form, in particular surfactants of any kind, hair conditioners such as, for example, cationic polymers, etc.

Another subject of the invention is a multi-compartment dyeing device or “kit” or any other multi-compartment packaging system, as described for example in U.S. Pat. No. 6,228,129, especially in column 26, lines 13 to 24, especially in column 26, line 26 to column 27, line 9, or. A first compartment which contains the composition (A) as defined above, an optional second compartment contains the composition (A′) as defined above, when it is present, and a third compartment contains the oxidizing composition (B) as defined above. These devices can be equipped with means which allow the desired mixture to be applied to the hair, such as the devices described in. French patent FR-2,586,913, the disclosure of which is specifically incorporated by reference herein.

An oxidizing agent, which may be added to the colouring compositions for carrying out the method according to the invention containing composition, comprises an oxidizing agent and a base.

Further, the colouring composition of the present invention comprises for this oxidizing agent containing composition customary adjuvant and additives.

The formulations are for example a solution, especially a thickened watery or watery alcoholic solution, a cream, foam, a gel, a powder or an emulsion.

In general, preference is given to a cream formulation, a gel formulation or a foam formulation, and especially a foam formulation.

But, if stability- or solubility-problems arise it may of advantage to use powder formulation as for example described in DE 197 13 698, page 2, line 26 to 54 and page 3, line 51 to page 4, line 25, and page 4, line 41 to page 5 line 59.

The oxidizing agent (calculated as hydrogen peroxide) is present in this composition in 0.5 to 12% by weight, in particular from 1 to 6% by weight based on the totals weight of the oxidizing agent containing composition.

The pH-value of the oxidizing agent containing composition is usually about 2 to 7, and in particular about 3 to 6.

An oxidizing agent free composition, which may be added to the colouring compositions for carrying out the method according to the invention, comprises a developer compound and a coupler compound and a reduction agent, or

a developer compound or/and optionally a reduction agent, or a coupler compound and a reduction agent.

Further, an oxidizing agent free composition may additionally comprise a direct dye as for example described in German Patent Application 199 59 479, column 3, line 12 to line 16.

Additionally, the oxidizing agent free composition usually comprises customary adjuvant and additives. Preferred are those, which are described in German Patent Application, in column 3, line 17 to line 41.

The pH-value of the oxidizing agent free composition is usually about 3 to 11, and in particular about 5 to 10, and most particular about 9 to 10.

For adjusting the pH-value organic or inorganic acids, as for example described in German Patent Application 199 59 479, column 3, line 46 to line 53 are suitable.

The colouring compositions for carrying out the method according to the invention may also be combined with hair dye compositions comprising an acid dye. Hair dye compositions comprising an acid dye are known. For example, they are described in “Dermatology”, edited by Ch. Culnan, H. Maibach, Verlag Marcel Dekker Inc., New York, Basle, 1986, Vol. 7, Ch. Zviak, The Science of Hair Care, chapter 7, pages 248-250, especially on page 253 and 254.

The hair dye compositions comprising an acid dye have a pH of 2-6, preferably 2-5, more preferably 2.5-4.0. If the pH is too low, the resulting composition may roughen the hair, scalp and hand skin due to an acid component in some cases. If the pH is too high, the penetration accelerating effect on the acid dye is lowered.

The colouring method according to the present invention may also readily be used in combination with other dyes and/or adjuvants used in the colouring of hair, for example

-   -   acid dye and an alkylene carbonate, as described in U.S. Pat.         No. 6,248,314, especially in examples 1 and 2, or     -   acid hair dye compositions comprise various kinds of organic         solvents represented by benzyl alcohol as a penetrant solvent         have good penetrability into hair, as described in Japanese         Patent Application Laid-Open Nos. 210023/1986 and 101841/1995,         or     -   acid hair dye compositions with a water-soluble polymer or the         like to prevent the drooping of the hair dye composition, as         described for example in Japanese Patent Application Laid-Open         Nos. 87450/1998, 255540/1997 and 245348/1996, or     -   acid hair dye compositions with a water-soluble polymer of         aromatic alcohols, lower alkylene carbonates, or the like as         described in Japanese Patent Application Laid-Open No.         53970/1998 and Japanese Patent Invention No. 23911/1973.

Preferred keratin fibers are human hair.

The dyes or dye precursors are suitable for all-over colouring of the hair, that is to say when colouring the hair on a first occasion, and also for re-colouring subsequently, or colouration of locks or parts of the hair.

The dyes or dye precursors are applied to hair for example through massage in by hand, a comb, a brush, or a bottle, or a bottle, which is combined with a comb or a nozzle.

In general, the dyes or dye precursors are applied to the hair in a formulation with further components, like adjuvants or additional dyes or dye precursors.

After the application of the dyeing composition the dyed hair is customary rinsed. Customary, the rinsing is conducted with water.

In a suitable embodiment of the methods of the present invention for dyeing human hair, the dyeing composition is not rinsed off, but washed off with a commercially available hair shampoo.

In general, the dyed hair is dried after rinsing and/or washing.

To colour keratin-containing fibres, especially to colour human hair, the compositions are usually applied to the hair in an amount of from 50 to 100 g in the form of the aqueous cosmetic carrier, left on the hair for approximately 30 minutes and then rinsed off or washed off with a commercially available hair shampoo.

Customary, drying is conducted with hot air by means of a drier or the like, since color migration to clothes and the like becomes scarcely caused.

In the context of the present invention, the expression “a further dye”, denotes preferably an oxidation dye, a diazotised compound, a capped diazotised compound and/or coupler compound, or acid dye, especially selected a cationic, anionic or uncharged direct dye.

A very suitable method for dyeing keratin fibers comprises contacting the keratin fibers under alkaline conditions with at least one capped diazotized compound and a coupler compound, with the proviso that the pH is adjusted in the range from 2 to 6 in the last method step.

Adjusting the pH is achieved in conventional manner by adding an acid as described for example in EP 962218, especially on page 3, lines 12 to 16.

Acids are for example tartaric acid or citric acid, a citric acid gel, a suitable buffer solution with optionally an acid dye.

Preferred technical forms of acids are a solution, a gel, a cream, foam, a conditioner, a emulsion, a shampoo and more preferred a shampoo or a conditioner.

In the context of the present invention, the expression “alkaline condition”, denotes to all method steps without those wherein acid conditions are explicitly described.

The methods of the present invention for dyeing keratin fibers, in particular human hair, comprise after contacting the keratin fiber with at least a dye of formulae (Ia) or (Ib) and a coupler compound.

Usually the hair is then left to stand, and afterwards rinsed.

A suitable method for dyeing is for example described in WO 01/66646 on page 15, line 32 to page 16, line 2.

Usually, the dyeing compositions are usually applied to the hair in an amount of from 50 to 100 g.

This composition is left on the fiber at 15 to 45° C. for 5 to 30 minutes, and in particular for 10 to 20 minutes at 20 to 30° C.

The method of colouring according to the invention in combination with at least one direct dye may comprise

-   -   a) contacting the keratin fibers with at least one direct dye, a         base and an oxidizing agent and a compound of formulae (Ia)         and/or (Ib) and a coupler compound.

Suitable compositions, which can be used in combination with the method for colouring according, comprising at least one direct dye and an oxidizing agent, are for example described in WO 97/20545, on page 3, line 24 to page 11, line 4, and especially on page 4, line 9 to 17.

The composition comprising at least one direct dye, a base and an oxidizing agent is prepared by mixing at least one direct dye and a base, and then just before the dyeing of the hair, adding an oxidizing agent.

Alternatively, the oxidizing agent can be applied simultaneously with a composition comprising at least one dye and a base.

Preferably, the method for dyeing keratin fibres with at least on direct dye comprises using a multi-compartment dyeing device or ‘kits’ as described for example in WO 97/20545, especially on page 4, line 19 to line 27.

Suitable methods for enlightening dyeing, which can be used in combination with the method for colouring according to the invention are described in WO 97/20545, on page 11 to page 13.

Further preferred methods for dyeing with cationic dyes, which can be combined with the method of colouring according to the present invention, are described

-   -   in WO 95/01772, especially on page 10, line 24 to page 11, line         16, and especially on page 11, line 29 to page 28, or     -   in WO 01/66646, especially on page 1, line 18 to page 3, line         16, and preferred from page 16, line 20 to page 22, or     -   in EP 970 685, especially on page 50, lines 15 to 43, and         preferred from page 50, line 46 to page 51, line 40, or     -   in DE-A-19 713 698, especially page 5, lines 26 to 60, or     -   a method of dyeing with direct dyes and oxidizing agent is         described in WO 97/20545, especially on page 10, line 10 to page         11, lirie 55 and preferably on page 11, line 6 to page 13, line         19.

Further preferred for dyeing with combinations of cationic dyes and other dyes, which can be combined with the method of colouring according to the present invention, are:

-   -   mixtures of at least two cationic dyes as described in WO         95/01772, especially on page 11, lines 1 to 15, or     -   combinations of Pyrazolo-[1,5-a]-pyrimidines with at least one         cationic dye as described in EP 998,908, especially on page 50,         lines 15 to 28, or     -   combinations of cationic dyes as described in FR-2788432,         especially on page 49, line 28 to page 52, and preferred on page         50, lines 16 to 28, or     -   combinations of direct dyes and/or an oxidation dye and         oxidizing agents in the form of permanent-wave fixing solution,         especially with direct dyes as described in DE-A-19 713 698,         especially on page 2, lines 12 to 23, especially on page 4, line         65 to page 5, line 59, or     -   combinations of cationic dyes and an oxidation dye of the         developer compound type and oxidizing agents as described in EP         850 638, especially on page 29, line 42 to page 30, line 20 and         preferred on page 30, line 25 to page 32, line 30, or     -   combinations of an extemporaneous mixture of a composition (A)         containing one or more oxidation dye precursors and optionally         one or more couplers, and of a composition (B), in powder form,         containing one or more direct dye, preferably cationic,         optionally dispersed in an organic pulverulent excipient and/or         a mineral pulverulent excipient, and a composition (C)         containing one or more oxidizing agent as described in U.S. Pat.         No. 6,190,421, especially in column 8, lines 43 to 52, and         preferably in column 8, line 55 to column 9, line 55, or     -   a ready-to-use composition comprising, at least one oxidation         base, at least one cationic direct dye and at least one enzyme         of 2-electron oxidoreductase type in the presence of at least         one donor for the said enzyme as described in U.S. Pat. No.         6,228,129, especially in column 25, line 56 to column 27, line         9, or     -   a ready-to-use composition or multi-compartment dyeing device         comprising compositions of at least one direct cationic dye and         at least one nitrated benzene dye as described in WO 99/20235 on         page 34, line 27 to page 37, or     -   a ready-to-use composition or multi-compartment dyeing device         comprising compositions of at least one direct cationic dye and         at least one autooxidisable oxidation dye, especially benzene,         indol and indoline derivatives as described in WO 99/20234,         especially on page 32, line 20 to page 35, oxidation dyeing         compositions of at least one direct dye and at least one         meta-Aminophenol derivative and at least one developer compound         and an oxidizing agent as described in EP 850 636, especially on         page 18, line 1 to page 22, line 11, or     -   oxidation dyeing compositions of at least one direct dye and at         least one developer compound selected from the group of         para-Phenylenediamine derivatives and Bis-Phenylalkylenediamine         and, and at least one coupler compound selected from the group         of meta-Diphenols and an oxidizing agent, as described in         EP-A-850 637, especially on page 19, line 24 to page 22, line         57,     -   cationic dye and e.g. a pyrazolo-(1,5-a)-pyrimidine derivatives,         as described in EP 998 908, especially on page 47, line 25 to         page 50, line 29, or     -   arianors and/or oxidative dyes, as described in FR-2 788 432,         especially on page 2, line 16 to page 3, line 16, and page 5,         line 19 to page 14, line 8, and combinations with cationic dyes         as described on page 14, line 23 and following, or     -   oxidative dye precursors (unsaturated aldehyde and coupler         compounds), as described in German Patent Application 197 172         24, especially on page 3, line 36 to page 9 line 64.

The method of colouring of keratin fibers, especially human hair, according to the present invention may be combined with direct dyes and oxidative dyes.

The method for dyeing keratin fibers with direct dyes and oxidative dyes, in particular human hair, comprises

-   -   a) contacting the keratin fibers with an oxidizing agent,         optionally containing at least a direct dye,     -   b) then contacting the keratin fibers with an oxidizing agent         free composition, optionally containing at least a direct dye,         or     -   a) contacting the keratin fibers with an oxidizing agent free         composition, optionally containing at least a direct dye,     -   b) then contacting the keratin fibers with an oxidizing agent,         optionally containing at least a direct dye;         -   with the proviso that independently from each other in at             least a single method step a) and/or b) a compound of             formulae (Ia) and/or (Ib) and a coupler compound is present.

The method of colouring according to the present invention may combined with a method for dyeing keratin fibers with direct dyes and oxidative dyes, which comprises

-   -   a) contacting the keratin fibers with at least one direct dye,     -   b) then contacting the keratin fibers with an oxidizing agent         free composition; with the proviso that independently from each         other in at least a single method step a) and/or b) a compound         of formulae (Ia) and/or (Ib) and a coupler compound is present.

Such method is for example described in DE 199 41 450, especially on page 5, lines 50 to 58, and on page 8, line 31 to 46.

Oxidizing agent is usually applied in form of an oxidizing agent containing composition. Oxidizing agent free composition containing at least one coupler compound, at least one developer compound, a base and a reduction agent.

Customary, the oxidizing agent containing composition is evenly applied in a sufficient amount related to the amount of hair, usually with 30 to 200 g.

In general, the oxidizing agent containing composition is left on the fiber at 15 to 45° C. for 0 to 15 minutes, and in particular for 0 to 5 minutes.

Then the oxidizing agent free composition is applied to the hair.

In general, the direct dye and oxidizing agent free composition is left on the fiber at 15 to 50° C. for 5 to 45 minutes, and in particular for 10 to 25 minutes.

The coupler and developer compounds of the oxidizing agent free composition can be applied simultaneously or in succession. Preferred is a simultaneous application.

One preferred embodiment of the method is to wash the hair with shampoo and or a weak acid, such as citric acid or tartrate acid.

The direct dyes, which are stable to reduction can stored together with the oxidizing agent free compositions and are applicable as composition.

It is of advantage to prepare compositions of direct dyes, which are not stable to reduction, with oxidizing agent free compositions just before the dyeing method.

Further, a direct dye and an oxidizing agent free composition can be applied simultaneously or in succession.

A suitable method for the coloration of keratin fiber with direct dyes and oxidation dyes, which can be used in combination with the method of colouring according to the present invention, comprises

-   -   a) mixing at least one direct dye and optionally at least one         coupler compound and at least one developer compound, and an         oxidizing agent, which optionally contains at least one direct         dye, and     -   b) then contacting the keratin fibers with the mixture as         prepared in step a);         with the proviso that independently from each other in at least         a single method step a) and/or b) a compound of formulae (Ia)         and/or (Ib) and a coupler compound is present.

A further suitable method for the coloration of keratin fiber with direct dyes and oxidation dyes, which can be used in combination with the method of colouring according to the present invention, comprises

-   -   a) mixing at least one autooxidable compound and at least one         developer compound and at least one direct dye, and     -   b) then contacting the keratin fibers with the mixture prepared         in step a); with the proviso that independently from each other         in at least a single method step a) and/or b) a compound of         formulae (Ia) and/or (Ib) and a coupler compound is present.

The direct dye is usually applied in form of a composition, comprising further adjuvants, in particular an aqueous composition.

In general the mixing is conducted just before contacting the keratin fibers.

Usually, the mixture prepared in method step a) is evenly applied in a sufficient amount related to the amount of hair, usually with 30 to 200 g.

In general, the mixture is left on the fiber at 15 to 45° C. for 0 to 50 minutes, and in particular for 30 to 45 minutes.

One preferred embodiment of the methods is to wash the hair with shampoo and or a weak acid, such as citric acid or tartrate acid, as for example described in EP 962218, especially on page 3, lines 9 to 18.

In addition, the method of the invention comprises further a two step, separate application of a direct dye and an oxidation dye. Such an application is for example described in DE-A-19 713 698, especially on page 4, line 65 to page 35, line 59, wherein the keratin fibres are contacted in a first step with a direct dye, especially in form of a tinting powder, and an oxidizing agent, and then, in a second step, with an oxidizing free composition, especially in form of a powder.

Further, it is possible to apply for example a ready-to-use composition for the combination of method according to the invention with the oxidation dyeing of keratin fibers, in particular human keratin fibers such as hair, as described in U.S. Pat. No. 6,190,421, in column 1, line 65 to column 3, line 65, especially in column 10, line 62 to column 12, line 65.

According to this method, the ready-to-use dye composition as defined above is applied to the fibers and is left on them for an exposure time preferably of from approximately 3 to approximately 40 minutes, more preferably from approximately 5 to approximately 30 minutes, after which the fibers are rinsed, optionally washed with shampoo, rinsed again and dried.

If unsaturated aldehydes are used as oxidative precursor dye together with a coupler compound no oxidizing agent is needed as described in German Patent Application 19 717 224.5. Nevertheless, it may be desirable to conduct the colouring in the presence of oxidizing agents, if lightening or a unified colouration of the keratin fiber is envisaged.

The method of dyeing keratin fibers with oxidative dye precursors, which can be used in combination with the method of colouring according to the present invention, comprises

-   -   a) contacting the keratin fibers with an unsaturated aldehyde, a         coupler compound and a direct dye; with the proviso that         independently from each other a compound of formulae (Ia) and/or         (Ib) and a coupler compound is present.

In all above-cited dyeing methods it is also possible to apply a mixture of coupler compounds/and or developer compounds and/different direct dyes.

Another preferred embodiment of the methods for oxidative dyeing of keratin fibers, which can be used in combination with the method of colouring according to the present invention, comprise applying to the keratin fibers after contacting with an oxidizing agent free composition containing a coupler compound and a developer compound and optionally a direct dye with a further oxidizing agent free composition containing a coupler compound and a developer compound and optionally an oxidizing agent containing composition and optionally a direct dye by a pH range from 5 to 7, preferred from 6.5 to 7. In general the keratin fiber is not washed or rinsed afterwards as for example described in EP 962217, especially on page 3, lines 9 to 17.

The developer and coupler compounds can be applied separately, simultaneously or in succession.

In all above-cited dyeing methods with oxidation dye precursors it is also possible to apply a mixture of coupler compounds /and or developer compounds.

A more suitable method for the dyeing of keratin fibers with oxidative dyes, which can be used in combination with the method of colouring according to the present invention, comprises,

-   -   a) contacting the keratin fibers with an oxidizing agent         containing composition,     -   b) then contacting the keratin fibers with an oxidizing agent         free composition; with the proviso that independently from each         other in at least a single method step a) and/or b) a compound         of formulae (Ia) and/or (Ib) and a coupler compound is present.

Such method is for example described in DE 19959479, especially in column 3, line 54 to column 4, line 8.

Usually, the oxidizing agent containing composition is evenly applied in a sufficient amount related to the amount of hair, usually with 30 to 200 g.

In general, the oxidizing agent containing composition is left on the fiber at 15 to 50° C. for 0 to 15 minutes, and in particular for 0 to 30 minutes.

Then the oxidizing agent free composition is applied.

Customary, the oxidizing agent free composition is left on the fiber at 15 to 50° C. for 5 to 45 minutes, and in particular for 10 to 25 minutes.

The coupler and developer compounds of oxidizing agent free compositions can be applied as an admixture, or separately simultaneously or in succession. Preferred is the application of an admixture.

One suitable embodiment of the methods is to wash the hair with shampoo and or a weak acid, such as citric acid or tartrate acid, as for example described in EP 962218, especially on page 3, lines 9 to 18.

A further suitable method for the coloration of keratin fiber with oxidation dyes, which can be used in combination with the method of colouring according to the present invention, comprises

-   -   a) mixing at least one coupler compound and developer compound,         and an oxidizing agent, and     -   b) then contacting the keratin fibers with the mixture as         prepared in step a); with the proviso that in at least a single         method step a) and/or b) a compound of formulae (Ia) and/or (Ib)         and a coupler compound is present.

A further suitable method for the coloration of keratin fiber with an oxidation dye, which can be used in combination with the method of colouring according to the present invention, comprises

-   -   a) mixing an autooxidable compound and a developer compound, and     -   b) then contacting the keratin fibers with the mixture prepared         in step a); with the proviso that independently from each other         in at least a single method step a) and/or b) a compound of         formulae (Ia) and/or (Ib) and a coupler compound is present.

Especially preferred is a method for dyeing keratin fibers, in particular human hair, with capped diazotised compounds, which comprises,

-   -   a) contacting the keratin fibers, under alkaline conditions,         with at least one capped diazotised compound and a coupler         compound, and optionally an oxidising agent, and optionally in         the presence of a further dye,     -   b) then adjusting the pH in the range of 6 to 2 by treatment         with acid, optionally in the presence of a further dye; with the         proviso that independently from each other in at least a single         method step a) and/or b) a compound of formulae (Ia) and/or (Ib)         and a coupler compound is present.

The capped diazotised compound and coupler compound and optionally the oxidizing agent, can be applied in any desired order successively, or simultaneously.

Preferably, however, the capped diazotised compound and the coupler compound are applied simultaneously, in a single composition.

Customary the dyeing composition is applied to the hair in an amount of from 50 to 100 g.

In the context of the present invention, the expression “alkaline conditions” denotes a pH in the range from 8 to 10, preferably 9-10, especially 9.5-10.

Adding bases, for example sodium carbonate, ammonia or sodium hydroxide, to the hair or to the dye precursors, the capped diazotised compound and/or the water-soluble coupling component, or to colouring compositions comprising the dye precursors, customarily achieve the alkaline conditions.

In the second stage, the diazotised compound and the coupler compound are then caused to react, preferably by lowering the pH to a value of from 6 to 2, especially from 3 to 4.

A preferred embodiment of all methods of the present invention for dyeing keratin fibers comprise contacting the keratin fibers under alkaline conditions with at least one capped diazotized compound and a coupler compound, with the proviso that the pH is adjusted in the range from 2 to 6 in the last method step.

Adjusting the pH is achieved in conventional manner by adding an acid as described for example in EP 962218, especially on page 3, lines 12 to 16.

Acids are for example tartaric acid or citric acid, a citric acid gel, a suitable buffer solution with optionally an acid dye.

Preferred technical forms of acids are a solution, a gel, a cream, foam, a conditioner, a emulsion, a shampoo and more preferred a shampoo or a conditioner.

The ratio of the amount of alkaline colouring composition applied in the first stage to that of acid colouring composition applied in the second stage is preferably about from 1:3 to 3:1, especially about 1:1.

This first alkaline and then acid dyeing compositions each are left on the fiber at 15 to 45° C. for 5 to 60 minutes, and in particular for 5 to 45 minutes at 20 to 30° C.

In the methods according to the invention, whether or not colouring is to be carried out in the presence of a further dye will depend upon the colour shade to be obtained.

In the context of the present invention, the expression “a further dye”, denotes preferably an oxidation dye, a diazotised compound, a capped diazotised compound and/or coupler compound, or acid dye, especially selected a cationic, anionic or uncharged direct dye, especially a cationic dye selected from the group of the cationic dyes as described in WO 95/01772, especially on page 2, line 7 to page 4, line 1, and preferred on page 4, line 35 to page 8, line 21 with the given preferences, and as described in WO 01/66646, especially on page 1, line 18 to page 3, line 16, or a mixture of at least two cationic dyes as described in WO 95/01772, especially on page 8, line 34 to page 10, line 22.

-   -   a) A preferred embodiment of the method of colouring according         to the present invention concerns the combination with capped         diazotised compounds and a coupler compound, comprises         contacting the keratin fibres with more than one capped         diazotised compound and/or more than one coupler compound in the         presence of at least a single compound of formulae (Ia) and/or         (Ib) and a coupler compound.

Preferred is a method of the present invention for the coloration of keratin fiber with capped diazotised compounds comprises

-   -   b) mixing, under alkaline conditions, at least one with capped         diazotised compound and at least one coupler compound and at         least one direct dye and optionally at least one developer         compound; and an oxidizing agent, which optionally contains at         least one direct dye, and     -   c) then contacting the keratin fibers with the mixture as         prepared in step a),     -   d) then adjusting the pH in the range of 6 to 2 by treatment         with acid, optionally in the presence of a further dye; with the         proviso that independently from each other in at least a single         method step a), b) and/or c) a compound of formulae (Ia) and/or         (Ib) and a coupler compound is present.

More preferred is a method for dyeing keratin fibres with at least one capped diazotized compound, which comprises

-   -   a) mixing under alkaline conditions, at least one capped         diazotized compound and at least one direct dye, a base and an         oxidizing agent, and     -   b) then contacting the keratin fibers with the mixture as         prepared in step a),     -   c) then adjusting the pH in the range of 6 to 2 by treatment         with acid, optionally in the presence of a further dye; with the         proviso that independently from each other in at least a single         method step a), b) and/or c) a compound of formulae (Ia) and/or         (Ib) and a coupler compound is present.

Further, preferred is a method for the coloration of keratin fiber with capped diazotised compounds comprising

-   -   a) mixing under alkaline conditions, at least one with capped         diazotised compound and at least one coupler compound and         optionally at least one direct dye and optionally at least one         developer compound, and optionally at least one autooxidable         compound, and     -   b) then contacting the keratin fibers with the mixture prepared         in step a),     -   c) then adjusting the pH in the range of 6 to 2 by treatment         with acid, optionally in the presence of a further dye;with the         proviso that independently from each other in at least a single         method step a), b) and/or c) a compound of formulae (Ia) and/or         (Ib) and a coupler compound is present.

A further suitable method for the two-step direct dyeing of keratin fibres, which can be used in combination with the method of colouring according to the present invention, is characterized in that,

-   -   a) contacting the keratin fibers with an oxidizing agent or an         oxidizing agent containing composition,     -   b) then contacting the keratin fibers with at least one capped         diazotised compound and at least a coupler compound and         optionally a direct dye or/and optionally an oxidizing agent         free composition,     -   c) then adjusting the pH in the range of 6 to 2 by treatment         with acid, optionally in the presence of a further dye. or     -   a) contacting the keratin fibers with at least one capped         diazotised compound and a coupler compound and optionally a         direct dye or/and optionally an oxidizing agent free         composition,     -   b) then contacting the keratin fibers with an oxidizing agent or         an oxidizing agent containing composition,     -   c) then adjusting the pH in the range of 5 to 2 by treatment         with acid, optionally in the presence of a further dye with the         proviso that independently from each other in at least a single         method step a), b) and/or c) a compound of formulae (Ia) and/or         (Ib) and a coupler compound is present.

The present invention also concerns a method for the colouration of keratin fibers, especially human hair, with acid dyes, which can be used in combination with the method of colouring according to the present invention.

The method comprises

-   -   a) contacting the keratin fiber with an acid dye in the presence         of a compound of formulae (Ia) and/or (Ib) and a coupler         compound.

Customary, the dyeing composition comprising an acid dye is applied to the hair in an amount of from 50 to 100 g.

This in a composition is left on the fiber at 15 to 45° C. for 1 to 30 minutes, and in particular for 0 to 15 minutes at 20 to 30° C.

Preferably the hair is rinsed and than washed with shampoo and more preferably not rinsed, but washed with shampoo.

The shampoo used herein includes a shampoo comprising 5-20% of a usual anionic surfactant such as an alkylsulfate or polyoxyethylene alkylsulfate.

The compositions according to the invention may furthermore comprise any active ingredient, additive or adjuvant known for such preparations.

The colorations obtained with by the method of dying keratin fibers according to the present invention are distinguished by outstanding fastness to washing properties.

The following Examples serve to illustrate the invention without limiting the invention thereto.

EXAMPLES

Method A:

A strand of bleached human hair is immersed, for 30 minutes at room temperature, in an aqueous solution which contains 0.4 mol/litre of diazonium salt D and which has been adjusted to a pH of 10.0 with a carbonate buffer. Excess solution is then removed from the strand, which is then immersed for 30 minutes in an aqueous solution buffered to pH 10.0 and containing 0.2 mol/litre of coupling component K. The strand is then thoroughly rinsed with water and dried in air. Hair coloured in the colours indicated in Table 1, having outstanding fastness properties, especially fastness to washing properties, is obtained.

Method B:

A strand of bleached human hair is immersed, for 30 minutes at room temperature, in an aqueous solution which contains 0.2 mol/litre of coupling component K and which has been adjusted to a pH of 10.0 with a carbonate buffer. Excess solution is then removed from the strand, which is then immersed for 30 minutes in an aqueous solution buffered to pH 10.0 and containing 0.4 mol/litre of diazonium salt D. The strand is then thoroughly rinsed with water and dried in air. Hair coloured in the colours indicated in Table 1, having outstanding fastness properties, especially fastness to washing properties, is obtained.

Method C:

A strand of bleached human hair is immersed, for 30 minutes at room temperature, in an aqueous/ethanolic (80:20) solution adjusted to pH 3.0 and containing 0.4 mol/litre of diazonium salt D and 0.2 mol/litre of coupling component K. Excess solution is then removed from the strand, which is then immersed for 30 minutes in a carbonate buffer solution adjusted to pH 10.0. The strand is then thoroughly rinsed with water and dried in air. Hair coloured in the colours indicated in Table 1, having outstanding fastness properties, especially fastness to washing properties, is obtained.

The greatest colour intensity is achieved using method A. TABLE 1 coupling component K

diazonium salt D

violet reddish-orange orange

reddish-blue red orange

Example 1

A strand of bleached white human hair is treated, at room temperature, with a composition comprising a diazonium salt of formula (IIIb), 1.18 g, dissolved in 10 ml of a solution of water and a non-ionic surface-active compound (Plantaren 2000®), the pH of which solution has been adjusted to 10 using citric acid.

After 30 minutes and after removing the excess composition, the strand is treated at room temperature with 10 ml of a composition comprising a coupling component (V), 0.38 g, dissolved in 10 ml of a solution of water and a non-ionic surface-active compound (Plantaren 2000®), the pH of which solution has been adjusted to 10 using citric acid.

After 30 minutes, the strand has a red shade which is still very intense even after shampooing ten times.

Example 2

A strand of mid-blond human hair is treated, at room temperature, with a composition comprising a coupling component (V), 0.38 g, and a dye, 0.01 g, of formula

prepared as described in EP 658 095, Example 2, in 10 ml of a solution of water and a non-ionic surface-active compound (Plantaren 2000®), the pH of which solution has been adjusted to pH 10 using citric acid.

After 30 minutes and after removing the excess composition, the strand is treated at room temperature with a composition comprising a diazonium salt of formula (IIIb), 1.18 g, dissolved in 10 ml of a solution of water and a non-ionic surface-active compound (Plantaren 2000®), the pH of which solution has been adjusted to 10 using citric acid.

After 30 minutes, the strand has a red shade which is still very intense even after shampooing ten times. The colour of the strand coloured in that manner is distinguished by very good washing fastness and light fastness both on damaged and on undamaged hair, especially permanent waves.

Example 3

A strand of bleached human hair is treated with a mixture of equal parts by weight (5 g in each case) of 6% hydrogen peroxide solution and of composition A. Composition A: cetyl stearyl alcohol 11.0 oleth-5 5.0 oleic acid 2.5 stearic acid monoethanolamide 2.5 coconut fatty acid monoethanolamide 2.5 sodium lauryl sulfate 1.7 1,2-propanediol 1.0 ammonium chloride 0.5 EDTA, tetrasodium salt 0.2 perfume 0.4 wheat protein hydrolysate 0.2 silica 0.1 2,5-diaminotoluene sulfate 0.7 4-amino-2-hydroxytoluene 0.5 2,5,6-triamino-4-hydroxypyrimidine 0.2 sulfate sodium sulfite 1.0 ascorbic acid 0.5 resorcinol (IV) 2.2 composition A: pH 9.8 water ad 100 g

After contact for 30 minutes at room temperature, 10 g of a mixture of equal parts by weight (5 g in each case) of 6% hydrogen peroxide solution and of composition B are applied to the strand. Composition B: cetyl stearyl alcohol 11.0 oleth-5 5.0 oleic acid 2.5 stearic acid monoethanolamide 2.5 coconut fatty acid monoethanolamide 2.5 sodium lauryl sulfate 1.7 1,2-propanediol 1.0 ammonium chloride 0.5 EDTA, tetrasodium salt 0.2 perfume 0.4 wheat protein hydrolysate 0.2 Aerosil ® 0.1 diazonium compound (IIb) 10.0 composition B: pH 9.8 water ad 100 g

After 30 minutes, the strand is rinsed out and shampooed.

A strong, intense, striking violet coloration having good fastness to washing and fastness to rubbing properties is obtained.

Example 4

A strand of blond human hair is treated with 10 g of composition A. Composition A: cetyl stearyl alcohol 11.0 oleth-5 5.0 oleic acid 2.5 stearic acid monoethanolamide 2.5 coconut fatty acid monoethanolamide 2.5 sodium lauryl sulfate 1.7 1,2-propanediol 1.0 ammonium chloride 0.5 EDTA, tetrasodium salt 0.2 perfume 0.4 wheat protein hydrolysate 0.2 Aerosil ® 0.1 diazonium compound (IIb) 10.0 composition A: pH 9.8 water ad 100 g

After contact for 30 minutes at room temperature, 10 g of composition B are applied to the strand. Composition B: cetyl stearyl alcohol 11.0 oleth-5 5.0 oleic acid 2.5 stearic acid monoethanolamide 2.5 coconut fatty acid monoethanolamide 2.5 sodium lauryl sulfate 1.7 1,2-propanediol 1.0 ammonium chloride 0.5 EDTA, tetrasodium salt 0.2 perfume 0.4 wheat protein hydrolysate 0.2 Aerosil ® 0.1 resorcinol (IV) 2.2 composition B: pH 9.8 water ad 100 g

After 30 minutes, the strand is rinsed out and shampooed.

A strong, intense, striking violet coloration having good fastness to washing and fastness to rubbing properties is obtained.

Example 5a

A strand of blond human hair is treated with 10 g of composition A according to example 4. After contact for 30 minutes at room temperature, 10 g of composition B, which additionally comprises

0.1 g of a dye of formula

prepared as described in WO 01/66646, Example 4, is applied to the strand. After 30 minutes, the strand is rinsed out and shampooed.

A strong, intense, striking violet coloration having good fastness to washing and fastness to rubbing properties is obtained.

Example 5b

Example 5b is the same as example 5a with the proviso that Basic Yellow 87 replaces the dye of example 4 of WO 01/66646.

Example 5c

Example 5c is the same as example 5a with the proviso that Basic Red 51 replaces the dye of example 4 of WO 01/66646.

Example 5d

Example 5d is the same as example 5a with the proviso that the dye of example 6 as described in WO 02/31056 replaces the dye of example 4 of WO 01/66646.

Example 6

A strand of bleached white human hair is treated, for 30 minutes at room temperature, with 5 g of a composition comprising resorcinol (IV) 2.2 diazonium compound (IIb) 10.0 benzyl alcohol 5 ethanol 20 lactide acid 3.5 sodium carbonate solution of pH 3 hydroxyethyl cellulose 1.5 water ad 100 g

The strand is then treated with a shampoo that has been adjusted to a pH of 10 by means of sodium carbonate and, after 10 minutes, is rinsed out.

The strand is coloured an intense violet.

Example 7

The following cream base is used to prepare a composition:

Cream Base:

-   10 parts by weight of fatty alcohols of chain length C₁₂-C₁₈ -   5 parts by weight of nonylphenol+9 parts by weight of ethylene oxide -   75 parts by weight of water

The cream base is further methoded to form the priming cream.

Priming Cream:

-   2 parts by weight of coupling component (VI) -   25 parts by weight of cream base -   5 parts by weight of ammonium chloride -   66 parts by weight of water

The resulting priming cream has a pH of 4.5.

Before application, the powdered diazonium salt is incorporated in the priming cream in the amounts indicated below to yield the composition.

Composition

-   98 parts by weight of priming cream -   2 parts by weight of diazonium salt (IIb)

The hair to be coloured is treated with the resulting composition for 10 to 20 minutes so that the composition penetrates. The azo coupling reaction is then brought about by applying an alkaline shampoo that has been adjusted to a pH of 9 by means of sodium carbonate. After from 5 to 10 minutes, the colouring is complete, and the coloured hair is washed and dried. The coloration obtained has an orange shade.

Example 8

The procedure is as in Example 7 except that, instead of coupling component (VI), a mixture of coupling components (V) and (VI) in equal parts by weight, that is to say one part by weight of each, based on the total weight of the priming cream, is used. The coloration obtained has a red-tinged orange shade.

Example 9

The procedure is as in Example 8 except that, instead of the diazonium salt (IIb), a mixture of the diazonium salts (IIb) and (IIIb) in equal parts by weight, that is to say one part by weight of each, based on the total weight of the composition, is used in the priming cream. The coloration obtained has a reddish-orange shade. 

1. A method of colouring keratin-containing fibres comprises applying at least one diazonium compound of formula Ia or Ib

wherein R₁ to R₅ are each independently of the others C₁-C₁₂alkyl, C₅-C₁₄aryl, C₅-C₈cycloakyl, C₆-C₂₀aralkyl, C₁-C₁₂alkoxy or C₁-C₁₂alkylthio unsubstituted or substituted by one or more halogen atoms, nitro, cyano or alkoxy groups; or hydrogen, halogen, hydroxy, nitro, COOH, SO₃H, CN, SCN, C₁-C₄alkylsulfonyl, phenylsulfonyl, benzylsulfonyl, di-C₁-C₄alkylaminosulfonyl, C₁-C₄alkylcarbonyl-amino, C₁-C₄alkoxysulfonyl or dihydroxy-C₁-C₄alkylaminosulfonyl, and X⁻ is O⁻, COO⁻ or SO₃ ⁻, and at least one coupling component to the material to be coloured and causing them to react at a pH in the range of 8 to
 12. 2. A method according to claim 1, wherein R₁ to R₅ are each independently of the others are hydrogen, SO₃H, halogen, nitro, CN or methyl.
 3. A method according to claim 1, wherein the diazonium compound is a compound of formula IIb or IIIb


4. A method according to claim 1, wherein the coupling component is a compound of formula IV, V or VI


5. A method according to claim 1 comprising applying an aqueous solution of at least one diazonium compound of formula Ia and/or Ib according to claim 1 to the fibre, and then applying an aqueous solution at least one coupling component to the fibre and causing them to react at a pH in the range of 8 to
 12. 6. A method according to claim 1 comprising applying an aqueous solution of at least one coupling component to the fibre, and then applying an aqueous solution of diazonium compound of formula Ia and/or Ib according to claim 1 to the fibre and causing them to react at a pH in the range of 8 to
 12. 7. A method according to claim 1 comprising applying an aqueous solution of at least one diazonium compound of formula Ia and/or Ib according to claim 1 and a coupling component to the fibre at a pH in the range of 1 to 6, and causing them to react at a pH in the range of 8 to
 12. 8. A composition comprising at least one diazonium compound of formula Ia or Ib according to claim 1 and an adjuvant.
 9. A composition comprising (a) at least one diazonium compound of formula Ia or Ib according to claim 1, (b) at least one coupling component, (c) an agent for adjustment of the pH in the range of 1 to 6, and (d) water.
 10. A method of colouring keratin-containing fibres, comprising applying a composition according to claim 8 and a coupling component to the fibre, and causing them to react at a pH in the range of 8 to
 12. 11. A method according to claim 1, comprising applying a diazonium compound of formula Ia or Ib, a coupler compound and/or at least one further dye.
 12. A method of colouring keratin-containing fibres, comprising applying a composition according to claim 9 to the fibre and causing them to react at a pH in the range of 8 to
 12. 